AGC Book 20% Cyan Karl Fischer Titration

GTP Brochure

Good Titration Practice™ in Karl Fischer Titration

EDITORIAL

Dear Reader METTLER TOLEDO has an excellent knowledge in any kind of moisture and water content determination from % to ppm. It is of crucial importance to select the right analytical method in order to obtain reliable results that ensure quality and properties of the products in a multitude of industries. Karl Fischer titration is the method of choice for water content determination. With the new generation of METTLER TOLEDO compact volumetric and coulometric Karl Fischer Titrators V20/V30, C20/C30 and Excellence combined general and volumetric KF titrators T70 and T90, water determination has reached an unrivaled level of simplicity and security. This helps you to perform your daily tasks in the most optimal way. In this brochure a specific focus is put on how to perform the Karl Fischer titration analysis the correct way. We would like to introduce this to you as part of ‘Good Titration PracticeTM (GTP) in Karl Fischer titration. This brochure comprises detailed background information and recommendations about: • • • • • Chemistry and control of the Karl Fischer titration Practical tips and hints on sample preparation and instrument operation Measures to optimize accuracy and precision of the water determination Selection of the optimal method for water determination of your specific sample Trouble shooting recommendations if results do not coincide with the expectations

This GTP brochure in combination with the application brochure 39 should serve you as powerful tools for trouble-free water determination throughout the whole lifetime of your METTLER TOLEDO KF titrator. We wish you great success and enjoyment

Hans-Joachim Muhr Market Support Manager BA Titration

Rolf Rohner Marketing Manager BA Titration

..21 3............................................................................................................METTLER TOLEDO Good Titration PracticeTM in KF Titration Contents 1 Fundamentals of the Karl Fischer titration ........................................................4 Polarization current and end point...6 Dissolving capacity of the solvent ...........1 Principle of bipotentiometric indication ....33 4.............................................................33 4.................................2 Concentration determination with di-sodium tartrate dihydrate.........................................19 3.................................2 Stoichiometry of the coulometric KF rection ...........3 Secure draining and filling of the titration cell: SOLVENT MANAGER...........2....5 Limitations for the use of the cell without diaphragm............................................................11 2.............................2...............................................................................................................28 4..........38 5 Sampling ...................4 Cleaning the coulometric KF titration cell.....................32 4............................................26 4..............7 2...................2 Coulometric KF analysis..........13 3..............2......2 Working with the coulometric KF instruments ..........................1............4 Special reagents for aldehydes and ketones.......1 How often should the concentration be determined?......1..36 4..........9 2...............35 4.......4 1..........................21 3...............5 Cleaning the measuring electrode .........16 3....27 4...........3.. The Karl Fischer titration..20 3............24 4.................2 The drift ..........3 Concentration determination with Water Standard 10..4...4 Generator electrode without diaphragm ........1 The Control Band ...........16 3.....26 4................................................4...........................................2 Two-component KF reagent .................................................39 1 ...............................................19 3.....................................................................................................7 2.......3 The Cautious start ...................................................................................................................................................1 The influence of atmospheric humidity (drift determination) .................1 Indication ...............................................1 Volumetric KF reagents...........................................................................................................6 General recommendations ....................6 Termination parameters for both coulometric and volumetric KF titration..........................................................4.............................3 Pyridine-containing reagents .................34 4.....................1....................................................29 4.........................................................................................................2 The Karl Fischer chemical reaction .............................1...................2.......................2....................1 One-component KF reagent .......18 3.....2..........13 3...................5 1....................4....................4.....................................................................................28 4.......................................19 3........2 Reaction rate .................................13 3.............................4 Control parameters in the volumetric KF titration ..............................................................29 4..............1...........2.........37 4.1 Filling the coulometric cell .....3 Consequences for practical applications..............3...........................22 3...............................1......1 An historic overview ..........1 Titration stand ..8 2..................................14 3.........................9 2...........2...........................................................................................2.....................................................................2 End point and polarization current...........8 2.................3 Volumetric KF Titration: Titrant concentration..........................3 Iodine generation.........3....................................................................6 2 Volumetric and Coulometric Karl Fischer Analyses .......12 3 Titration control and end point determination............................................0 mg/g .......................2 The minimum and maximum dosing rate ...........2 When do you have to replace the electrolyte? ..4 Concentration determination with pure water..............................7 2..............................................................1...................11 2....4 1................3 Stirring speed and dispersion of the volumetric KF titrant...4......1............................................................5 Control paramaters in the coulometric KF Analysis ........5 Karl Fischer reagents with ethanol ......2...........................8 2.6......................1 KF coulometry ....................5 Application tips ..............26 4............................1 Using and optimizing the termination parameters for both volumetric and coulometric KF titration ...............................3.......................................................................................................10 2.....3....................1............................................................................33 4...................................3...............9 2......................................................................5 The solvent.................................18 3.........................................................................................................................................

.............................................................................................................................3 Technical products – organic ........................1 Organic and inorganic chemicals ..................................................................58 7.......1 Reaction with methanol.............5 Accessories for sample input ...............................39 5........4...1 Volumetric methods ................83 11.................................inorganic .......................................................2 Foods and technical products ....................................5 Determination of water in gases ...............5 Technical natural products ................77 11..............73 10.....................................................................................54 7.............62 8 Measurement results ..........................................................67 8...2 External extraction .......................................................85 11....................................................................................................METTLER TOLEDO Good Titration PracticeTM in KF Titration 5........................................................87 11......................................................58 7.........3 Amount of sample .......2 Purge gas........................3.86 11...........43 6................................................1 Resolution and detection limit .........................................................................................................................70 9....................................................................................................................................................86 11...........................................3 Repeatability ..............................................79 11.............................49 7.....................47 7.....4..........................................4............................................87 11...........................5 STROMBOLI automatic oven sample changer ...............83 11................................................................................................81 11.....................1 Taking the sample..................................................................................79 11.6 Determination using the drying oven ............................................................................60 7...................2 Inorganic chemicals ..........43 6........4.................1 Solid samples.88 11........................39 5..................................................................................4 Sample preparation and input .............................6......................................................................78 11.....................4.................................................................................................2..........................................................................................................68 9 Interferences ..............67 8.....................1..........................71 9...............2 Side reactions ..............................................75 11 Karl Fischer Titration: The Method at a Glance .........................................................................6........................................................................................71 9......................................................................90 2 ..........................58 7................................2 Solids: Sample input ...............................................................................45 7 Release of water from the sample .........................3 Liquids: Characteristics ..................................................3 External dissolution .....1...............................................................................................................................................3 Reaction with iodine .................................1 Principle ..............2 Coulometric methods .....................................70 9.................................71 9.................................77 11...................................................................................................................................4 Lyophilized substance in septum bottles...................................................................4.............................89 12 Appendix .........77 11...........................6 Food ..................................1...................................................................................................6...............................2.................................................................................................................................................................................................6........80 11.........................................................1 Organic Chemicals..................2 Volumetric Karl Fischer Titration .........4 Liquids: Sample input.59 7..........................................................................................48 7...................57 7..........2 Solid samples.................73 10.....1 Solids: Characteristics................................6............1...78 11............................1 Coulometry.......................................................................................................................................................................................1...........................................................................................79 11................................................................2..................1 Effects of temperature.....40 6 Sample addition ....................3 Titration Methods .........87 11........1 Internal extraction ................86 11.................72 10 Troubleshooting ..........................................................2 Measurement accuracy................................................2 Storing the sample ..3............................................5 Additional literature ........6 References.............70 9...67 8...............4 Example: reevaluation of side reactions ..........................................................................55 7..................1 Liquid samples ...................................................................................................2 Reaction with water..........................................................2 Liquid samples ................................4 Manual Karl Fischer drying oven......2.........................................................1..3 Procedure.........................................4 Technical products ........................................80 11......................................................................................................................................................................................................................

......95 12...............6............................6............................................................90 12.........................................1 For samples soluble in methanol or ethanol ...............................96 12......................METTLER TOLEDO Good Titration PracticeTM in KF Titration 12.....2 Formula for the external dissolution .......................1 Formula for the external extraction .......................4 For ketones and aldehydes..................................................................................................93 12.......................95 12..........................2 Two-component reagent: ................................................................................98 13.........................................93 12..................................................3 For samples that are insoluble in methanol or ethanol ...........98 13.98 13............4 For ketones and aldehydes..............................5 Water Standards for Karl Fischer volumetric titration...............91 12........................................................................1 One-component reagent .6..........................4 Reagents and solvents for coulometric analysis ..................95 12..4.............................................................................................92 12.................................92 12...6..............................6 Titrants and solvents for volumetric analysis ...........5 For acids and bases (pH value) ........4.............................................................94 12.5 For acids and bases (pH value) .....6............3 For samples insoluble in methanol or ethanol............................................................2 For samples poorly soluble in methanol or ethanol.........2 For samples that are poorely soluble in methanol or ethanol ......3 Reagents for coulometry: ....................................................4 Safety data for the KF-components and auxiliary solvents: ...............4..................................98 3 ....................97 13 Hazards and waste disposal tips ...........................96 12...........3 Standards for Karl Fischer coulometry...........1 For samples that are soluble in methanol or ethanol ....91 12......................92 12...................................................................4.........................98 13.95 12............................4...

Publication: “The Dead-Stop End Point“. First fully automatic KF titration with laboratory robots (METTLER DL18 and ZYMARK).Boyd [4]. Peters and J. respectively. and solvent dispensing and removal.0. D. Introduction of less poisonous KF reagents based on ethanolic solution.3 First titrator (METTLER TOLEDO DL55) with online curves E = f(t) and V = f(t) for Karl Fischer titration. First German DIN standard for the Karl Fischer titration (DIN 51777. Hopkinson [2]. L.1 mg/g) with test certificate according to DIN 50049-2. Solid KF Oven Standards with water contents of 5. M. Introduction of the METTLER TOLEDO DL32/39 KF Coulometers (generating cell with and without diaphragm). Meyer and C. April 1956. Improved METTLER TOLEDO DO307 KF Manual Drying Oven. Pyridine-containing two-component reagents and dead-stop titration instruments are commercially available. 1. Introduction of the METTLER TOLEDO Titration Compact Line V20/V30 and C20/C30 Karl Fischer Instruments. Pyridine-free KF reagents are commercially available. Introduction of the METTLER TOLEDO STROMBOLI KF Oven Sample Changer. Eberius [3]. First microprocessor controlled KF titrator (METTLER DL18) with automatic drift compensation. 0. Use of Karl Fischer method spreads. S.0. “Testing of mineral oil hydrocarbons and solvents: Determination of water content according to Karl Fischer . First diaphragm-less cell for coulometric KF titration.J. Jungnickel. Publication on stabilized single-component Karl Fischer reagent by E.1 1935 1943 1950 1952 1955 1956 An historic overview Publication: "Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern" by Karl Fischer [1]. and DL67/70ES/77 Titrators Introduction of the METTLER TOLEDO DL31/DL38 KF Titrators with dedicated fuzzy logic control. DL37 KF Coulometer from METTLER TOLEDO. promoted by publications by E. METTLER TOLEDO RONDO Sample Changer with Karl Fischer Kit for automated KF volumetric determination. 1959 1960 1970 1980 1984 1985 1989 1990 1995 1997 1998 New DV705 KF Titration Stand with very low drift value (< 2μg/min) for the METTLER TOLEDO DL53/55/58. 2000 2001 2002 2008 4 . Enormous spread of the use of KF titration. Wernimont and F. Automatic KF titration instruments with piston motorized burettes. DO185 Drying Oven for the DL18 Karl Fischer Volumetric Titrator. First coulometric KF titration instruments are commercially available. titrant specific standard parameters and LEARN titration.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1 Fundamentals of the Karl Fischer titration 1. Publication: Coulometric Karl Fischer Titration by A.5% and 1%.Direct method”). by G. They replaced the DL18/35 KF Volumetric Titrators. Water standards (10.

METTLER TOLEDO Good Titration PracticeTM in KF Titration 1. Bryanz and Mitchell [6] formulated a two-step reaction: 1. but rather the methyl sulfite ion. Py•SO3 + H2O → 2 Py-H+I– + Py•SO3 – Py-H+HSO4 – Further studies conducted by J. In an alcoholic solution. I2 + SO2 + 3 Py + H2O → 2. the 5 . The rate of the Karl Fischer reaction. I2 + SO2 + 3 Py + H2O → 2.e.5. the maximum reaction rate is reached here and cannot increase further. it only acts as a buffering agent and can therefore be replaced by other bases. the reaction between iodine and water takes place in the stoichiometric ratio of 1:2: 1. i. At pH values above 8. Barenrecht [7] on the subject of the Karl Fischer reaction have revealed that: • • Pyridine is not directly involved in the reaction. Smith. it is necessary to neutralize the acids that are formed during the process (HI and H2SO4). W. Verhoff and E.5 to 8. the more methyl sulfite is formed by the capture of protons. In the pH range 5. the reaction between iodine and water takes place in the stoichiometric ratio of 1:1. Methanol proved to be suitable as a solvent. Karl Fischer used pyridine for this purpose. In order to achieve an equilibrium shift to the right.. Py•SO3 + CH3OH → 2 Py-H+I– + Py•SO3 – Py-H+CH3SO4 According to these equations. In an alcohol-free solution. depends on the pH value of the medium (see graphics below) -d[I2]/dt = k • [I2] • [SO2] • [H2O] One possible explanation for the influence of pH on the reaction rate is that it is not the sulfur dioxide itself that is oxidized by iodine under the influence of water. C. and the faster the rate of the Karl Fischer reaction.2 The Karl Fischer chemical reaction I2 + SO2 + 2 H2O → 2 HI + H2SO4 The water content determination is based on the reaction described by R. This is formed from sulfur dioxide and methanol according to the equation: 2 CH3OH + SO2 → CH3OH2+ + CH3OSO2- The higher the pH of the solution. methanol not only acts as a solvent but also participates directly in the reaction itself. all the sulfur dioxide is present as methyl sulfite. described by the rate constant k. Bunsen [5]: Karl Fischer discovered that this reaction could be used for water determinations in a nonaqueous system containing an excess of sulfur dioxide [1].

Studies by E. Verhoff and E. Scholz developed a pyridine-free Karl Fischer reagent with imidazole as base [8]. • Influence of the water content of the sample on the Karl Fischer reaction The water content of the sample also influences the H2O:I2 molar ratio. A. methanol) (e. Scholz was also able to confirm the existence of basic methylsulfite in methanol/SO2/I2 solutions during the titration. E. you can use other alkohols such as.g. Methanol should therefore always be present in the minimum required amount.g. 2-propanol. Experiments on the stoichiometry of the reaction showed that methanol can in fact be replaced by other alcohols (e.3 • Consequences for practical applications Influence of pH on the Karl Fischer reaction Since the maximum rate of the Karl Fischer titration is in the pH range 5.5 to 8. however. J. for determination in ketones or aldehydes).g. Scholz resulted in the following reaction scheme being proposed for the Karl Fischer reaction [8]: 1. and for bases: salicylic acid). pH values less than 4 and greater than 8 should be avoided in practice. ethylene glycol monomethyl ether. Barendrecht [7] observed an increase in the titer with water contents greater than 1 mol/L. On the basis of this knowledge. If a methanol-free titrant has to be used (e. but also facilitated faster and more accurate titrations because imidazole buffers in a more favorable pH range than pyridine. This. and references therein]. This reagent not only replaced the toxic. → → (RNH) · SO3 R (RNH) · SO4 R + 2 (RNH)I 1.g. • Influence of the solvent on the Karl Fischer reaction The stoichiometry (molar ratio of H2O:I2) depends on the type of solvent: Alcoholic solvent Non-alcoholic solvent H2O:I2 = 1:1 H2O:I2 = 2:1 (e. Seubert [9] identified methylsulfite in KF solutions with the aid of IR spectroscopy and isolated and identified methyl sulfate as the secondary product of the KF reaction. ROH + SO2 + RN 2. 6 . you should adjust the pH value to the ideal range by adding buffering agents (for acids: imidazole. diethylene glycol monoethylether) [10. this results in a more sluggish endpoint and higher iodine consumption. dimethylformamide) Studies by Eberius [3] showed that iodine and water react in the ratio of 1:1 if the percentage of methanol in the solvent is 20% or more. methoxyethanol. in a titration. for instance. pungent pyridine. With acidic or basic samples. is not a serious limitation because the water concentration in the solvent is usually much less. ethanol. This improves the titer stability.C. (RNH) · SO3 R + 2 RN + I2 + H2O This resulted in the general chemical equation: ROH + SO2 + 3 RN + I2 + H2O → (RNH)•SO4 R + 2 (RNH)I E.METTLER TOLEDO Good Titration PracticeTM in KF Titration reaction rate increases due to side reactions between iodine and hydroxide or methylate ions. In 1988.

The reagent can be stored for approximately two years. sulfur dioxide and imidazole. Coulometric Karl Fischer Analysis. Suitable for samples where water is present in trace amounts: 1 ppm . Suitable for samples where water is present as a major component: 100 ppm . You can also use a methanolic solvent mixture specially adapted to the sample as the solvent. dissolved in a suitable alcohol.100% Coulometric Karl Fischer Analysis Iodine is generated electrochemically during titration.1. 1 mg/mL for samples with a water content of less than 200 ppm.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2 Volumetric and Coulometric Karl Fischer Analyses The determination of the water content according to Karl Fischer is nowadays performed by two different techniques: – – Volumetric Karl Fischer Titration. where a solution containing iodine is added using a motorized piston burette. The solvent is methanol.e. 2 mg/mL for samples with a water content of less than 1000 ppm.5 mg/mL per year in a sealed bottle. where iodine is generated by electrochemical oxidation in the cell The selection of the appropriate technique is based on the estimated water content in the sample: Volumetric Karl Fischer Titration Iodine is added by a burette during titration.1 Volumetric KF reagents 2.5% 2.1 One-component KF reagent The titrant contains iodine. The reagent is available in three different concentrations: 5 mg/mL for samples with a water content of 1000 ppm to 100%.. The drop in titer. is approximately 0. the decrease in concentration. 7 . i.

Reagents One-component Two-component 2. apura® (CombiTitrant 5 Keto with CombiSolvent Keto. titration speed slower. whereas the solvent contains 2-chloroethanol and trichloromethane. sulfur dioxide and 2-methoxyethanol. 2 mg/mL for samples with a water content of less than 1000 ppm. – Titer less stable.g. such as amines. stable titer. Solvent capacity restricted. Both the components are very stable in storage.g. + Simple handling. methanol. which allow for fast and accurate Karl Fischer titrations. favorably priced. increases their lifetime. e. HYDRANAL® (Composite 5K and Working Medium K. Two-component reagent: The titrant contains iodine dissolved in an alcohol. methanol). sulfur dioxide and pyridine. provided that the bottle is tightly sealed. e. 2. imidazole and methanol. pyridine.3 Pyridine-containing reagents Despite the existence of pyridine-free reagents. High titration speed. Special methanol-free KF one-component reagents such as e.2 Two-component KF reagent The titrant contains iodine and methanol. from VWR/MERCK) are commercially available to prevent this problem. It is available in two different concentrations: • • 5 mg/mL for samples with a water content of 1000 ppm to 100%. imidazole. A titration speed two or three times as high can be achieved with the two-component reagent. additional water is produced and titrated at the same time. methanol) and B (iodine. or an alcoholic mixture. leading to higher water contents and a vanishing end point.4 Special reagents for aldehydes and ketones Aldehydes (R-CHO) and ketones (R-CO-R) form acetals and ketals if titrated with standard methanol-containing reagents. This reagent is declared as “rapid”. dissolved in methanol. and results in higher titration speed.g. The titration takes slightly longer than with the standard KF reagent. The solvent contains sulfur dioxide. imidazole. from Sigma-Aldrich) and e. The titrant has a stable titer.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2. To improve stability. Note that it may be necessary to adapt the end point value in the titration method to these reagents.1. Some manufacturers have slightly increased the pyridine content in the titrant to achieve a higher titration speed. One-component reagent: The titrant contains iodine. whereas the solvent consists of sulfur dioxide and a base.1. As a result.g. 8 . some manufacturers also sell the titrant separated into solution A (sulfur dioxide. reagents containing pyridine are still used because they are cheaper and can be made in-house. These solutions are mixed 1:1 just before use to form the one-component titrant. The separation into titrant and solvent improves stability of the KF reagents. This special reagent is also suitable for substances that react with methanol.1. The solvent is either methanol or consists of methanol mixtures. dissolved in an alcohol (usually methanol). One-component reagent: The titrant contains iodine.

however.5 Karl Fischer reagents with ethanol Since ethanol is less toxic than methanol.→ I2 + 2 e Iodine generation occurs at a generator electrode* (also called “generator cell”.2. ROH + SO2 + 3 RN + I2 + H2O → (RNH)•SO4 R + 2 (RNH)I In coulometry. The generator is close to the measuring electrode*. which is monitoring the potential of the sample solution by voltametric technique during coulometric titration. The classical coulometric cell consists of two parts. ethanol-based reagents were launched in 1998. The titrant contains iodine and ethanol.1. two-component. diethanolamine and ethanol. whereas the solvent contains sulfur dioxide. imidazole. 9 . a double pin platinum electrode.1 KF coulometry Coulometric KF determination of water is based on the standard reaction equation for the KF reaction. These reagents also allow for titration of several ketones which form ketals considerably more slowly in ethanol than in methanol. or “inner burette”) incorporated into the glass titration cell. * The terms "generator electrode" and "measuring electrode" mean an arrangement of two electrodes (anode and cathode) to form an electrolytic cell. the anode compartment and the cathode compartment. the iodine is generated electrochemically by anodic oxidation in the coulometric cell according to the following half-reaction: 2 I . 2.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2.2 Coulometric KF analysis 2. Both parts are separated by a diaphragm.

In Karl Fischer reaction two iodide ions.e. as chloroform.2. is the quantity of charge that is transported by a current of 1 ampere in one second. the positive hydrogen ions are reduced to hydrogen.METTLER TOLEDO Good Titration PracticeTM in KF Titration The anode compartment contains the anolyte. The cathode compartment contains the catholyte. The value 96845 C/mol is known as the Faraday constant. are oxidized to one molecule of iodine. To calculate it.→ H2 + 2 RN Ammonium ions are then reduced with the formation of hydrogen and a free amine. Depending on the application. Note that methyl sulfonic acid. the reagent that enables completion of the whole electrochemical reaction: the oxidation reaction in the anolyte compartment is completed by a reduction reaction in the catholyte compartment. iodine reacts with water. present in the anolyte compartment.g. 2 I.→ I2 → H2O 10 . can reach the cathode where it is reduced to a sulfide compound (obnoxious smell!). CH3SO3H. i. An ammonium salt is added to the catholyte in order to promote hydrogen production. The catholyte is either a manufacturer-specific special reagent.2 Stoichiometry of the coulometric KF rection The amount of water titrated by coulometric technique is determined by the amount of electrical current given in Coulomb. The negative iodide ions release electrons at the anode and form iodine. Anode reaction At the anode. I2. other solvents such e. it is necessary to first recall the definition of 1 Coulomb: one coulomb. Subsequently. or the same reagent as used in the anode compartment. This is the main product formed. which subsequently reacts with water. the KF electrolyte which is required for the oxidation in order to generate iodine by applying a current at the generating electrode. 1C=1A·1s On the other hand. hexanol or ethylene glycol may be added. To avoid this. Methanol or ethanol is used as solvent.e. the catholyte should be replaced once in two weeks. 2 [RN]H+ + 2e. 2. 96485 C of current are needed. i. imidazole and iodide salts. used to generate iodine. This consists of sulfur dioxide. it is known that to produce one mole of a chemical substance that requires one electron. This can cause the cathode to become black. C. I-. releasing two electrons at the anode. C. iodine is generated from iodide by electrochemical oxidation. Cathode reaction At the cathode. octanol.

2. the conductivity of the anolyte is influenced by the samples and additional solvents (chloroform. For an electrochemically optimized Karl Fischer cell. 2. less than 3–4 μS/cm). coulometry is designated as absolute method.2. At very low conductivities (i. The main advantages compared to cells with diaphragms are: no contamination or blockage of the diaphragm easier cleaning lower drift 11 . the coulometer operates with current pulses of 400 mA. it is used as a reference method for the determination of water content. it is strongly recommended that the coulometer is regularly checked by measuring a certified water standard. no standardization of the coulometric KF reagents is necessary.712 C electrical current. 300. For this reason. this calculation can be expressed as follows: 1 mg of water corresponds to a consumption of 10. In addition.e. Nevertheless.015 g/mol.3 Iodine generation Iodine is generated by means of current pulses of 400. 200 and 100 mA. Since the molar mass of water is 18. Since current and time can be accurately measured. The maximum pulse height depends on the following factors: conductivity of the anolyte voltage at the generator electrode surface of the generator electrode The voltage at the generator electrode and the surface of the electrode depend on the type of coulometer. the current conversion efficiency for iodine production is assumed to be 100%. hexanol. 2 x 96485 C/mol is required for 1 mole of water. etc. 2. This gives an iodine generation rate which corresponds to a maximum of 2240 μg water/min. With standard conductivity values. As a consequence. The rate of iodine generation is adjusted by varying the pulse duration and frequency and the pulse height (in mA).4 Generator electrode without diaphragm with diaphragm without diaphragm The first commercially available diaphragmless cell for KF coulometry was introduced in 1989. the maximum possible current applied by the instrument is 100 mA.).METTLER TOLEDO Good Titration PracticeTM in KF Titration Therefore.

phenols (most) esters .edible oils petroleum oils A cell with diaphragm is required for: samples with a very low water content (< 50 μg water/sample) very accurate determinations nitro compounds unsaturated hydrocarbons. may also be reduced at the cathode by the formation of water. Nevertheless.ethers ketones (with special reagent) . R-NO2 + 3 H2 → R-NH2 + 2 H2O Besides this. In practice. Nascent hydrogen is formed at the cathode. it is still possible for a very small amount of iodine to reach the cathode. other easily reducible substances such as unsaturated fatty acids.5 Limitations for the use of the cell without diaphragm The cell without diaphragm is not suitable for samples that are easily reduced. The purpose is to prevent that iodine molecules generated at the anode are immediately reduced to iodide ions at the cathode instead of reacting with water. especially when easily reducible. 2. The diaphragmless cell is ideal for the determination of the water content of the following compounds: hydrocarbons . and for very accurate determinations.acetamides etheric oils and essences . this makes it almost impossible for iodine to reach the cathode and be reduced to iodide. Thus. the cathode is a small-size pin).g. for measurement of samples having a very low water content (e. However.2. 12 . This effect is further enhanced by the small dimensions of the cathode. The cathode is smaller and made in such a way that iodine cannot reach the cathode (i.. a relatively high stirrer speed allows for more rapid distribution of the generated iodine molecules. a different geometry is used for the generating cell without diaphragm. Note that hydrogen gas generated at the cathode is forming gas bubbles around its surface. lower than 50 μg water/sample). the cell with diaphragm may yield more precise results. This is a very good reducing agent.chlorinated hydrocarbons alcohols . the generator cell was first built with a porous ceramic frit (diaphragm) separating the inner cathode compartment from the anode compartment. In addition. The latter can thus react more efficiently with water. To avoid this concurring reaction.METTLER TOLEDO Good Titration PracticeTM in KF Titration Originally. especially for nitro compounds such as nitrobenzene. etc.e. the relative error due to this effect can be minimized by using a larger amount of sample.

there is no free iodine in the titration/anolyte solution. and the addition or production stopped exactly at the end point.the stirring speed and mixing of the sample solution. there will be free iodine in the titration solution. The control of the titration is only possible if the end point is indicated.the reaction rate of the Karl Fischer reaction . the titration is terminated.the control algorithm and its parameters. • • As long as the added iodine reacts with the water. Ideally. and hence. 3.the termination of the analysis. .METTLER TOLEDO Good Titration PracticeTM in KF Titration 3 Titration control and end point determination The addition or generation of iodine must be controlled. 13 .1 Indication 3. A high voltage is necessary to maintain the specified polarization current at the electrode.1. When the voltage drops below a defined value. constant AC current – the polarization current "Ipol" – is applied to a double pin platinum electrode. The resulting titration speed depends on the following factors: . iodine should be added or generated as quickly as possible.the addition speed or generation rate of iodine . • • • As soon as all the water has reacted with iodine. Free iodine causes ionic conduction and the voltage needs to be reduced to keep the polarization current constant. Only then can the titrant consumption or the generated iodine amount be determined with the desired accuracy.1 Principle of bipotentiometric indication A bipotentiometric indication is used for the volumetric Karl Fischer titration as well as for the coulometric analysis (in electrochemical terminology this is also called "2-electrode potentiometry"). A small. the water content. .the viscosity of the solution and its temperature. .

The iodine is present only at low concentration. If mixing is poor. Iodide ions. then releases the electron again at the positively charged platinum pin and is again oxidized to iodine. Ionic conduction Iodine takes up an electron at the negatively charged platinum pin of the indicator electrode and is thereby reduced to iodide (I-). no iodine reaches the negatively charged platinum pin.2 End point and polarization current The Karl Fischer titration is terminated when an excess of iodine is detected in the titration cell. free iodine is present in the titration/anolyte solution.(to a lesser extent) the type of electrode (i. The two negatively charged iodide ions are attracted by the positively charged platinum pin. Thorough mixing of the titration/anolyte solution is necessary in order to achieve constant "ionic conduction". .e. 14 . this value depends on the polarization current.METTLER TOLEDO Good Titration PracticeTM in KF Titration • The ionic conduction takes the following course: an iodine molecule is attracted by the negatively charged platinum pin. It then acquires two electrons and turns into iodide ions (2 I–). Above all. This leads to a termination of "ionic conduction" and the measurement signal becomes unstable. At the end of the titration: As soon as all the water in the sample has reacted with the iodine. where they donate the electrons and form an iodine molecule. the titration end point is reached if the potential at the polarized platinum double pin electrode drops below a specific predefined value. Ipol . there is no free iodine in the titration/anolyte solution. geometry and dimensions of the metal parts) . respectively. again.the solvent or anolyte used in the instrument. The end point value mainly depends on . Now a low voltage of 50 mV to 100 mV is required to keep the polarization current constant.e. I2. • • At the beginning and during the titration: As long as the iodine generated reacts with the water. This drop in voltage is used to indicate the end of the titration. i.the polarization current.1. This free iodine gives rise to "ionic conduction". 3. 400 mV to 650 mV is necessary to maintain the set polarization current at the double pin electrode. A voltage of ca. which are present in excess in the titration solution.

the following end points have been defined for methanolic one-component and two-component KF reagents using a V20/V30 volumetric KF titrator or T70/T90 Excellence titrator (double pin platinum electrode. exhibit a smaller potential jump. a layer is formed on the surface of the platinum pin sensor. Sensors with a large platinum surface. exhibit a larger potential jump and also a higher end point. Which polarization current should be used? A higher polarization current requires a larger iodine excess (indicated by a pronounced yellow coloration of the titration cell solution) to achieve ionic conduction for the determination of the end point. a lower polarization current gives a smaller and steeper potential jump at the end of the titration. a double ring or plates instead of rings. i. The current density can be compared to a water pipe where a specific water has to flow. This makes it more difficult to stop the titration at the right moment. pin length: 3 . With use.g. its surface can easily bond suitable chemical compounds.e. In general the larger the platinum surface the smaller the current density. and increases the risk of over titration. As a consequence. the lower the pressure needed to transport the desired amount of water through the pipe (= smaller pressure difference). pin diameter: 1 mm): AC Polarization current / µA 24 Endpoint / mV 100 For the coulometric KF analysis. i. iodine excess should be as low as possible to get accurate results. Sensors with short platinum pins (< 3 mm). On the other hand. with longer pins. the following values have been obtained with a C20/C30 KF Coulometer (double pin platinum sensor. and subsequently it remains constant. The layer is formed during the first ten titrations. this leads to a larger potential jump compared to a cleaned or a new sensor (without layer). 15 . e. The larger the diameter of the pipe. The condition of the sensor has an influence on the potential jump Platinum is a strongly adsorbing metal. Influence of the sensor The potential jump at the end of the titration is also influenced by the geometry (surface and design) of the platinum sensing material of the sensor.4 mm. the polarization current should be set as low as possible. just after the equivalence point. pin diameter: 1 mm): AC Polarization current / µA 5 Endpoint / mV 100 The same end point values can be used for ethanol based KF coulometric reagents. However. and increases the sensor resistance. With used sensors.e. pin length: 3 to 4 mm.METTLER TOLEDO Good Titration PracticeTM in KF Titration For the volumetric KF titration. on the other hand.

sulfur dioxide is present in large excess in the anolyte. lower reaction rates are achieved with anolyte solutions that have been used for a long time. On the other hand.the water concentration. note that sulfur dioxide is added only in slight excess with the iodine titrant solution when using one component titrant.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3. If the speed is too slow.3 Stirring speed and dispersion of the volumetric KF titrant Good mixing is essential for fast and accurate KF titrations. If 16 . 3.and on the iodine concentration. which gives a high reaction rate. 2. [H2O] .2 Reaction rate The reaction rate of the Karl Fischer titration depends on: . Example (V20/V30/T70/T90): One-component reagent Two-component reagent 2-3 min with a titrant consumption of 2. Towards the end of the titration.2 min with a titrant consumption of 2. It is consumed with each additional measured sample leading to a decreasing dioxide concentration. with the twocomponent reagents. 3. Iodine generation or addition is usually the rate determining factor. This results in a reaction rate up to 2 times faster for the two component reagent than for the one component reagent.0 mL 1. the titration may also be too slow. stirring speed. point of titrant addition (volumetric KF titration). the water concentration is lower. and the reaction rate also decreases: iodine must be generated or added more slowly because a small water amount is still present. [I2] .the sulfur dioxide concentration. Karl Fischer titrations with the two component reagent are thus significantly faster than with the one component reagent. [SO2] . a large excess of sulfur dioxide is present in the solvent. and overtitration may occur. shape of the vessel (volumetric KF titration). As a consequence. irregular. Mixing is influenced by the 1. the pH value of the solution has a strong influence on the rate and in particular on the stoichiometry of the Karl Fischer reaction. Iodine generation or addition can proceed rapidly because iodine immediately reacts with water. In the volumetric KF titration. the water content is high.5 . At the beginning.d[I2] / dt = k · [I2] · [SO2] · [H2O] In addition.0 mL In the coulometric KF analysis. Stirring speed The optimum stirring speed is obtained when a distinct vortex is visible.

Bubbles falsify the measured values. the stirring speed is too fast. leading to slower addition and longer titration time. Vessel shape The conical shape of the beaker and the short stirring bar lead to turbulence at the point of titrant addition that effectively disperses the titrant. Point of titrant addition The titrant should be added where the turbulence is the greatest to ensure efficient mixing. Iodine would not be distributed upwards. 17 . If a longer stirring bar is used.METTLER TOLEDO Good Titration PracticeTM in KF Titration bubbles form into the solution. but rather along the base directly towards the sensor. This is essential for a fast reaction rate and for short titration times. Otherwise the sensor may directly detect added iodine. Furthermore. turbulence is not achieved and the mixing effectiveness is lower. the point of addition should be sufficiently far away from the sensor to allow for sufficient time for reaction.

4 Control parameters in the volumetric KF titration Several parameters can be defined in the titration method in order to optimize the method for the samples and the reagents.1 The Control Band The control band is a modifiable control parameter for both types of KF reagents. The following drawing reveals a schematical illustration of the control band: 18 . Cautious The volumetric KF methods of the V20/V30 as well as T70 and T90 use KF titrant specific titration control parameters. The dynamic behaviour of the control can be influenced by a variation of the control band.4. An overview of the control parameters is given as follows: Volumetric KF Titration End point Control band Dosing rate (max) Dosing rate (min) Start: Normal.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3. The recommended standard values are listed in the following table: Recommended standard values Sensor Ipol [µA] Stirrer speed [%] End point [mV] Control band [mV] Dosing rate (min) [µL/min] Dosing rate (max) [mL/min] Start Driftstop relative [µg/min] 1-Comp titrant 24 35 100 400 80 5 normal 15 2-Comp titrant 24 35 100 400 100 3 normal 15 3.

With large amounts of water. 3. the titration will take too long. however. the titration starts so quickly that overtitration may occur.e.g. 3. In both cases (normal and cautious mode) the maximum dosing rate will be reached at the end of the ramping up. the control reacts more sensitively to potential changes.2 The minimum and maximum dosing rate Both rates limit the dosing speed of the titrant to an upper or lower level. if the control band width is decreased. the end point must be adjusted.METTLER TOLEDO Good Titration PracticeTM in KF Titration The titrant addition is calculated on one hand by using the distance of the actual potential from the end point and on the other by using dE/dt. The 2-Comp titrant control reacts more sensitively to a potential drop than the 1-Comp titrant control. 19 .4. Burette size [mL] 1 5 10 20 Maximum dosing rate [mL/min] 3 15 30 60 Remark: Since the maximum dosing rate of a 1 mL burette is lower than the standard parameter 5 mL/min in the case of a 1-Comp titrant.4 Polarization current and end point Each end point is valid for a specific polarization current. the slower is the titrant addition. at higher water contents.4. which leads to a stronger reduction of the dosing speed. Dosing rate (max) = 2 mL/min. Thus. e. The end point for a specific polarization current is influenced by the sensor and the solvent. You can also set the maximum dosing rate to a lower value for small amounts of water if you wish the titration to progress more cautiously. the titrator automatically issues a warning. the titration starts with a slower acceleration (ramp up) than in the normal mode.The dynamics of the control can be influenced in the following way: Increase of the control band Aggressive control Smooth control Two different controls are used for 1-Comp and 2-Comp titrants. In this case you can activate the Start: Cautious parameter. 3.4. This is more suited for small water amounts. In the cautious mode. Recommendations 1. The closer the potential to the end point. longer titration times and poorer repeatability are resulting by selecting a higher end point potential value. sensors with very short platinum pins (< 3 mm). 2. i.3 The Cautious start If the water content is very low.. In particular. if the polarization current changes. The maximum dosing rate is dependent on the actual burette size. The following points represent possible contributing factors: contaminated or old sensors. You should select Start: Cautious for one and two component reagents if the amount of water in the sample is less than 500 µg.

the overall ionic conductivity is decreased. • If 1-comp titrants are used. 3. Composolver E) the standard 1-Comp parameters (cf.METTLER TOLEDO Good Titration PracticeTM in KF Titration - long alkyl chain alcohols. which will lead to long titration times and to low precision. • • If 1-Comp titrants are used with Ethanol (e. If one-component reagents are used. Auxiliary reagents • If formamide is added to the solvent.4. 2-propanol. the titration can be accelarated by reduction of the control band to 300 mV. this results in an illdefined titration end point. the system reacts slowly in the case of ethanol based reagents. 20 . e. This measure allows the system to cope with the reduced conductivity. If 2-comp ethanolic reagents are used.g. setting up of the titrant as 1-comp KF titrant yields shorter titration times. the maximum dosing rate can be set higher for certain reagents: 4 mL/min for Riedel de Haen 2-Comp 5. The consequences of choosing a too low end point value are illustrated in the figures above: On the right side. the titration curve is more or less flat towards the end. the control band shall be decreased to 100 mV and the maximum dosing rate decreased to about 50%. table) work fine. In order to achieve a good repeatability. used as solvent. This results in a lower voltage required to maintain the polarization current. Therefore it is recommended to decrease the polarization current to about 15 μA. Therefore the potential jump at the end of the titration is smaller compared to conventional reagents. the sensor current shall be reduced to 15 μA. up to 8 mL/min for most 2-Comp 2 titrants.5 Application tips Methanol based reagents • The standard parameters listed in the table above are ideal for the titration with methanol-based reagents. • If Chloroform or Xylene is added in order to dissolve oil samples. Ethanol-based reagents • Compared to the methanol-based reagents. instead of methanol or ethanol. • If 2-comp titrants are used. the overall ionic conductivity is increased.g.

Furthermore it is recommended to reduce the polarization current to a value of 15 μA. 100 mA) 21 . 2. 3.4. 3. However the control band shall not exceed the start potential. 300. The most straight forward influence on the control behaviour is achieved by a variation of the maximum dosing rate. This control is also recommended for 2Comp systems that show a noisy signal at the beginning of the titration. In the case of 2-comp reagents over titration can be prevented by reduction of the maximum dosing rate. which is the case in some ethanolic reagents.METTLER TOLEDO Good Titration PracticeTM in KF Titration KF reagents for ketones • An end point value of 150 mV for both one-component and two-component reagents is recommended when using special KF reagents for aldehydes and ketones. If the titration takes too long. an increase of the control band is recommended. Fix (400. Cautious Generator current: Automatic. where the methanol has been replaced by e. The minimum dosing rate shall be used to fine tune the final phase of the titration.6 General recommendations 1. which is the case in 1-Comp systems.5 Control paramaters in the coulometric KF Analysis An overview of the relevant control parameters is given as follows: End point Control band Rate: Normal. 2-methoxyethanol. In general.g. ->Use the 1-Comp control Smooth system behaviour ->Use the 2-Comp control t 3. There is no need to accurately adjust the control band to the actual start potential. the 1-Comp control is suitable for systems that show an oscillating potential behaviour. E E t Oscillating system behaviour. In most cases 300 – 400 mV are well-suited. 200.

In particular. less than 50-100 μg water per sample). maximum titration time. More specifically. In addition. i. pulse frequency and pulse height (mA) are used as variables by the instruments. This parameter shortens the titration time and leads to repeatable results. the slower is the generation of iodine. Initially. absolute drift stop. Five termination parameters can be defined in the titration method: delay time.e. it has been possible to reduce the delay time to 5 to 10 seconds due to the introduction of • • • new.e. high resolution burettes (0. During the course of the titration it increases up to the maximum rate at a generating current of 400 mA.. Normal: This iodine generation mode is generally used for all water content determinations.25 µL for a 5 mL burette).METTLER TOLEDO Good Titration PracticeTM in KF Titration The iodine generation rate in the C20/C30 Coulometric Compact Karl Fischer Instruments depends on the distance from the end point. the pulse height can be automatically changed by the system if in the titration method the control parameter “Generator current” is set to “Automatic”. 300. The iodine generation starts slowly. minimum titration time 22 . iodine is generated by means of current pulses of 400.g. 200 and 100 mA. Later on. relative drift stop. and improved KF titration stands (i. Cautious: Suitable for samples of low water content (e. tightly sealed stand). Since the first developed KF reagents reacted slowly. as soon as the was potential value was lower than the set end point during the defined delay time. the online determination of the drift during analysis has enabled a so-called "drift stop" to be used as a termination parameter. the iodine generation is higher than in the cautious mode.e.6 Termination parameters for both coulometric and volumetric KF titration The KF titration can be terminated using various parameters. i. The fixed setting is used for solutions that exhibit a difficult characteristic with respect to conductivity. or it can be set to a specific value (“Generator current” . the slope of the iodine generation is steeper and the rate is increased based on the measured potential value. then the titration was stopped.e. The coulometer provides two different modes for iodine generation under the control parameter “Rate”: 1. During the course of the titration it increases up to the maximum rate at a generating current of 400 mA. i. Variation of pulse length (time). The closer the measured potential value from the predefined end point is. a delayed switch-off time of 10 to 20 seconds was set at the end point. pyridine-free reagents with a faster reaction rate.Fix). the slope of the iodine generation rate is flat at the beginning of the titration. 3. 2.

Typical delay time: 5 . 15 s) following the addition or generation of iodine. has to be t/s • Relative drift stop The titration is terminated as soon as the actual drift drops below the sum of the initial drift (i. Disadvantage: The value optimized to the initial drift. otherwise the termination criterion will never be reached. After the defined time has elapsed.METTLER TOLEDO Good Titration PracticeTM in KF Titration Delay time The titration is terminated when the potential remains below the end point for a defined time (e. Disadvantage: The minimum rate must be adapted to the initial drift and the titrant concentration. The smallest increment must be sufficiently large to compensate the drift.g.e. easy to understand (volumetric). the titration is terminated and the result is printed. the absolute drift stop value must be greater than the initial drift.Maximum titration time The titration is terminated after the defined time.15 seconds (Coulometric/Volumetric) • • Advantage: well-known method. especially if working with the KF sample oven. • Advantage: This parameter ensures a high repeatability of the results. titrant concentration (volumetric) and side reactions. 10 µg/min (volumetric) • Advantage: Independent on the titrant concentration. . otherwise the termination criterion is never satisfied. 5-15 μg/min (volumetric) • Advantage: independent on the initial drift. Typical absolute drift stop value: 3 µg/min (coulometric).m the drift before titration) and the relative drift. Thus. 23 . Absolute drift stop Termination occurs as soon as the actual drift drops below the predefined absolute drift value. Typical value for the relative drift stop = 2-5 μg/min (coulometric).

you can ignore these traces. A relative drift stop of 20 to 40 µg/min shortens the titration time without affecting the repeatability. you can terminate the titration at a higher drift (relative drift stop = 40 to 70 µg/min).6. the drift at the end is often greater than the initial drift.. The reason for this is either a very slow release of the last traces of water or a slow thermal decomposition of the sample. i. Use the drift/time curve to determine this value.Minimum titration time Titration is not to be terminated before this time in [s] is reached (exception: the maximum volume has been reached). A relative drift stop of 20 to 30 µg/min shortens the titration time. soluble samples You should normally choose the relative drift stop as a termination parameter. but involves a risk that the titration will be terminated a bit too early. This termination parameter is also well-suited when the internal extraction is needed to determine the water content in insoluble sample: The water contained in insoluble samples is extracted during the titration.e. Maximum titration time for determinations with the KF drying oven When using the drying oven. 3. This is particularly critical in connection with the "slower" reagents for ketones and aldehydes. It is recommended to be used for substances that release water slowly. possibly resulting in poorer repeatability and lower water contents. This parameter is independent of the the initial drift (coulometric. The vaporization of water is also irregular in the final stages.METTLER TOLEDO Good Titration PracticeTM in KF Titration . so 24 . Two-component reagent: A relative drift stop value of 5 to 15 µg/min is an optimum value for achieving good repeatability. Thus. • Advantage: This parameter ensures a high repeatability of the results. and the titrant concentration (volumetric). The value of the relative drift stop influences the repeatability and the titration time: • • Drift stop (low value) → better repeatability poorer repeatability → → long titration time short titration time Drift stop (high value) → In particular. the following values are recommended for volumetric KF titration: One-component reagent: A relative drift stop value of 5 to 15 µg/min is an optimum value for achieving good repeatability. this is the simplest and most universal parameter to use. volumetric). The final traces are only extracted very slowly. If the water content is relatively high.1 Using and optimizing the termination parameters for both volumetric and coulometric KF titration The following termination criteria are most commonly used for water determination by Karl Fischer titration: Relative drift stop for trouble-free.

A combination of the relative drift stop and the maximum titration time has proved effective for such samples. the titration is terminated at the latest after the defined maximum time. the maximum titration time has proven to be best termination criterion in practice. Note: To obtain accurate and reliable results you should only work with the coulometer when the drift is lower than 10 µg/min. If the drift is greater than 10 µg/min. Therefore. you should take measures to reduce the drift. Relative drift stop/maximum titration time for problematic samples Some samples lead to a high drift value at the end of the titration.METTLER TOLEDO Good Titration PracticeTM in KF Titration that the repeatability of the titration termination using the drift stop parameter is poor. (Set the minimum titration time equal maximum titration time). 25 . This is the case with samples that only release the final traces of water very slowly or that produce side reactions. If the drift stop value is not reached. The higher drift is therefore influenced to a large extent by the sample. It gives you the best accuracy and repeatability of results.

The desiccant absorbs the moisture and protects the titration cell against the ingress of moisture. When you assemble the titration stand for the first time. The air-conditioning system should therefore be equipped with a moisture condenser. i. The assumption that air-conditioned rooms have a lower atmospheric humidity is often not true: the majority of air-conditioning systems simply cool the air. The factors include: • • • • the atmospheric humidity the working medium the pH of the sample the side reactions between the sample and the Karl Fischer reagent 4.1. 26 . The Karl Fischer titration Various factors must be taken into account with Karl Fischer titration to obtain correct results. where the relative humidity can achieve values of more than 80%. there will be moisture on the glass surface of the titration cell and the inserts. whereas molecular sieves require temperatures up to 300 °C. until it is absolutely free of water. After the anolyte (coulometer) or the solvent (volumeter) has been added. Moisture can enter the sample. the titrant and the titration stand. Briefly. the relative humidity increases.e. This problem is particularly relevant in tropical climates or in coastal regions. the higher the atmospheric humidity in the laboratory. The air within the titration vessel also contains moisture. since cold air cannot absorb as much moisture.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. The total moisture can be titrated more quickly by gently moving the vessel from side to side so that solvent swirls up the side of the vessel to pick up moisture adsorbed on the glass walls. the residual moisture dissolves more rapidly into the anolyte (solvent).1 The influence of atmospheric humidity (drift determination) Atmospheric humidity represents the most relevant source of error in Karl Fischer titration. Silica gel can be regenerated over night at 150 °C.4 weeks (indicated by a colour change of the indicator of the silica gel). The drying capacity of the desiccant is limited and it depends on the humidity and can be exhausted after 2 . it is titrated to dryness during pretitration. Do not shake too vigorously to avoid solvent gets on the cover of the vessel. the greater is its influence on the results of the Karl Fischer titration. The drift. The following rules should be observed: • • Close all openings in the titration stand. This can take 1 . Condition the titration cell before use.1 Titration stand The titration stand must be sealed as tightly as possible against atmospheric moisture. In this way. • Protect the titration cell with a desiccant (3 Å molecular sieve and silica gel).3 hours. However. however. The Karl Fischer titrator should never be installed close to a ventilator of the air conditioning system! 4. remains high because the moisture present on the glass walls and the air in the titration cell diffuse only slowly into the anolyte (solvent).

it is necessary to quantify the amount of water entering the titration cell during titration. or it can be entered by the user (“Request”): Source for Drift Online Determination Fix value Request Explanation Last measured value of standby The drift is determined and stored as raw result DRIFT A fixed value is defined into method The value can be entered immediately after starting sample titration The drift value is subsequently used in the calculation of the result in order to compensate for the moisture that entered the titration cell according to the following formula: Sample result = Total amount of water determined .(drift * titration time). it is also possible to use the value of a previously performed drift determination (“Determination”). the KF titrator continuously titrates the water that diffuses into the cell. For accurate results. or a fixed value can be defined into the titration method (“Fix value”). and its value is displayed on the screen. if it is defined as the parameter “Source for drift: Online” in method function “Titration stand (KF stand)”. t. Therefore it must be taken into account when calculating the water content. In this respect. At the start of a sample titration. On the other hand. the drift indicates the quantity of water that enters the titration stand over a defined period. this water amount is also titrated during analysis. In the standby titration. traces of water will always find a way into the titration cell. the drift value should therefore be as low as possible and stable before the start of a titration! 27 . the last measured drift value is automatically stored.2 The drift No titration stand is completely water tight. On the other hand. This is achieved by titration of the dry solvent for a defined time (drift determination).METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. and is given in μg water/minute. Therefore.1.

• Titration cell with diaphragmless generator electrode . If the level of the catholyte is the same or higher. As soon as the stirrer is switched off.The difference in level between the anolyte and catholyte is maintained as long as the stirrer is in operation.2.Make sure that the level of the anolyte is approx.The generator electrode should dip approx. the levels slowly become the same. 2.Take approx. when the drying oven is used. Note: In production. 100 mL electrolyte solution (anolyte) into the titration cell. The catholyte always contains traces of water. Higher anolyte level → low drift Lower anolyte level → drift is high . In this case.5 mm higher than that of the catholyte.Pour approx. 5 mL from the bottle with a syringe and inject it into the generator electrode or empty an ampoule of catholyte into the generator electrode. the level of the anolyte drops due to evaporation. However. 100 mL anolyte. If this is not the case. a flow occurs from the cathode compartment to the anode compartment. you must add some methanol or sample so that the color changes to yellow. . . the level of the anolyte increases. some anolyte solutions contain an excess of iodide and the solution has a brown colour.5 cm into the electrolyte solution. which leads to a higher drift. 3 . 2. .When a sample is injected into the anode compartment.1 Filling the coulometric cell • Cell with generator electrode with diaphragm .Then fill the anode compartment with approx. . . By ensuring that the level of the anolyte is higher than the one of the catholyte. the anolyte should be topped up from time to time with anhydrous methanol. the moisture enters the diaphragm and is slowly released into the anode compartment.2 Working with the coulometric KF instruments 4. Normally this brown coloration disappears on filling the titration cell because the iodine excess is consumed. This can be avoided as it follows: 1. 28 . The catholyte can be dehydrated with a few drops of a volumetric KF one component titrant.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4.First transfer 5 mL catholyte to the cathode compartment.

• • • • • 4. the worse the stirring efficiency will be. A level sensor in the waste bottle prevents from overflow. the level of the solvent or the anolyte exceeds the 150 mL mark.2 When do you have to replace the electrolyte? The electrolyte must be replaced in the following situations: • If the capacity of the electrolyte is exceeded.Anolyte solutions (100 mL): after 1000 mg water. it is common use to replace both the anolyte and catholyte at the same time If after adding samples. .2. Any contact with the reagent is avoided during draining and refilling of the titration cell. when using a generator electrode with diaphragm. e. If an emulsion forms in the anode compartment. If the drift is too high. the drift slowly increases.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. After being used for two weeks.3 Secure draining and filling of the titration cell: SOLVENT MANAGER The easiest and secure way of draining and filling the coulometric titration cell is performed with the external KF liquid handling device Solvent Manger. In the cathode compartment sulfides and mercaptans are formed that lead to an obnoxious smell and a higher drift.g. The working principle of the Solvent Manager is illustrated in the following schematical illustrations: 29 .Catholyte solutions (5 mL): after 200 mg water. This can happen if large amounts of samples of low conductivity are titrated. If an electrolyte is used for a long period without replacement.2. If the conductivity of the anolyte drops to a very low value. below 10 μS. . The higher the level in the anode compartment. the dissolving capacity of the anolyte (coulometric KF) is exhausted and an emulsion is formed. This can lead to wrong results. With poorly soluble samples. In practice. The capacity is monitored by the coulometers (see operating instructions). The Solvent Manager is located on top of the waste bottle and includes strong air pump (diaphragm pump) and an electromagnetic valve. and the risk of over titration increases. It is fully controlled by the titrator.

30 . Step 2: The Anolyte is drained into the waste bottle by applying vacuum. Step 1b: Start the reagent replacement either from the manual function ‘Replace reagent’ or from a predefined Shortcut on the Home screen of the Touchscreen.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 1a: Put the draining and reagent refill tube into the coulometric titration cell.

Depending on the type of the generator cell the following liquid handling actions can be performed: Diaphragmless generator cell: Replacement of the anolyte Generator cell with diaphragm: Replacement of the anolyte and draining of the catholyte 31 . An optional reagent exchange set consisting of tubes. In this configuration only draining of the titration cell is possible. drying tube and tube holder enables both draining and refilling. The Solvent Manager is part of the standard delivery of the C20 and C30 Compact coulometric KF titrators.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 3: The pump direction is switched by activation of the magnetic valve and subsequently fresh solvent is pumped into the titration cell by applying over pressure of dry air. Step 4: After a predefined time or by manual interaction the pressure within the solvent/anolyte bottle is relieved by switching the magnetic valce into the initial position.

the most effective cleaning agent is chromic acid. . which leads to a higher drift.This procedure should be repeated at least once. Drying is not necessary if you use it immediately. .METTLER TOLEDO Good Titration PracticeTM in KF Titration Note: The tubes for anolyte exchange are not left in the titration cell during titration.Methanol flows through the diaphragm into the cathode compartment. Moisture and contaminants are rinsed out of the diaphragm. The C30 provides a reagent monitoring routine which is called Reagent Control. Afterwards dry the vessel at 100 °C in an oven or with a hot air drier.2. Afterwards thoroughly rinse the generator electrode with water. If immediate use is required rinsing with anhydrous methanol shall be applied. Simple cleaning and drying of the generator electrode Method A: . • Cleaning the titration vessel Clean the titration vessel with water or a suitable solvent. The generator electrode with diaphragm must be cleaned periodically because contamination accumulates in the diaphragm over a longer period of time. Place the empty generator electrode in the chromic acid or fill the generator electrode with chromic acid and let it flow through. Methanol flows through the diaphragm and rinses out moisture and contaminants. reagents can be replaced directly out of running method Choice of enforcing the user to replace it immediately or ask again later 4. . • Thorough cleaning of the generator electrode If the generator electrode and the diaphragm are strongly contaminated. then with anhydrous methanol and dry it as described above. Method B: . • 32 . It provides the following: Monitoring three reagent parameters Usable life in days Capacity in mg water Number of samples When due.4 Cleaning the coulometric KF titration cell The titration cell and both electrodes should be cleaned.Place the empty generator electrode in anhydrous methanol. since it would cause a higher drift value. especially if dirty samples are analyzed.Fill the generator electrode with anhydrous methanol.Afterwards dry the generator electrode at a maximum temperature of 50 °C in an oven or with a hot air dryer. The procedure is identical to that described above. The contaminants can originate from samples or are side products that have been formed in the cathode compartment by reduction.

We recommend to determine the titrant concentration daily. In the global settings within the setup menu of 33 . Their volume increases considerably with temperature. it is better to determine the concentration every 2 to 4 hours. The Ohmic resistance of the electrode is increased. The volumetric KF titrators enable monitoring of the usable life and life span of the titrant. 2) Connect the S7 connection of the generator cell with the indication electrode.5 mol/L sulfuric acid. repeatable results. In countries where the temperature varies considerably during the course of the day and the lab is not air-conditioned. The titrant may absorb moisture from the atmosphere reducing its concentration (the anhydrous methanol in the titrant is very hygroscopic) . As already described.01 mg/mL per week. 4.2. This leads to a higher potential jump. 4.5 Cleaning the measuring electrode Generally. However. the one-component titrant.3 Volumetric KF Titration: Titrant concentration The titrant concentration can change due to the following reasons: 1. while the two-component titrant is rather stable).if the desiccant on the titrant bottle is "used up". In this case. 3) Stop the method when the cleaning is finished so that the polarization current at the indication electrode is stopped. a layer is formed on the platinum surface after the first few titrations. 3.1 How often should the concentration be determined? How often the concentration is determined depends on the choice of titrant. the tightness of the titrant bottle and the desired level of accuracy. • With heavily contaminated electrodes. e. The tightness of the titration stand and the proper functioning of the burette and the end point indication are also checked at the same time as the concentration is determined. . the measuring electrode must be cleaned. so that there is a sharp drop in concentration.if the titrant bottle is not tightly sealed. This is sufficient in most cases. place the electrode in 0. a weekly titer determination would be sufficient (the concentration of the one-component titrant changes by 0. 2. Based on the chemical stability of the titrant. This also becomes noticeable through a dark coloration of the anolyte at the end point. A reminder can be set to warn the user at the start of every titration that the usable life is about to expire in the predefined time range (days). the indicating electrode does not need cleaning.3.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. • Clean the platinum pin with a paper tissue. This test of the complete system by a titer determination is therefore an essential condition for accurate. A significant change in temperature may occur: The Karl Fischer titrants consist of approximately 90% methanol or ethanol. which prevents a good indication.g. The layer should therefore not be removed by cleaning. and let an electrical current of about 400 mA flow across the platinum pins for 60 s by starting the KF titration: 1) Disconnect the S7 connection of the indication electrode. The titrant is not chemically stable. samples may be deposited on the surface of the electrode.

it contains 15. Rinse the burette 2 times into a waste bottle before you determine the concentration. is the primary standard for Karl Fischer titration since it is stable and non-hygroscopic. Either the user is simply warned or the usage of the expired titrant is blocked.Use the optimized METTLER TOLEDO method M301 Weigh between 0.2 Concentration determination with di-sodium tartrate dihydrate General Di-sodium tartrate dihydrate. Mix for 3 minutes to achieve complete dissolution before you start the titration.: . . Na2C4H4O6•2H2O (M = 230.and at the same temperature.METTLER TOLEDO Good Titration PracticeTM in KF Titration the titrator actions can be defined that will be applied if the usable life or life span is actually exceeded. This sample size yields an optimum titrant consumption of 1. Note: 1. i. Make sure that nothing adheres to the beaker wall or to the electrode. Since it slowly dissolves in methanol. Under normal conditions.5 mL with a 5 mL burette.08 g/mol). Determine the concentration under the same conditions as for sample analysis.66% of water. thus the titrant concentration slightly but continuously decreases slightly when left to stand for a long time. 4.04 and 0. The plastic tubing is not absolutely water vapor-tight. you should first grind it to a fine powder before using it or use special Di-sodium tartrate dehydrate for Karl Fischer Titration Procedure . i. 2.3. which prevents the execution of further titrations.using the same titration stand with the same volume of solvent.08 g di-sodium tartrate dihydrate with the aid of a weighing boat.e.e. - 34 . 26-50 % of burette volume.3 to 2. Add it into the titration vessel. Determine the weight by back weighing and enter it as sample size.

5 g of water standard 10. Less soluble. mixing time 2 to 3 minutes. Slightly soluble. mixing time 1 minute. mixing time 5 minutes. mixing time 1 minute. You must perform the determination in pure methanol! Highly soluble.0 mg/g General Water standards consist of a mixture of organic solvents containing a specific amount of water. You cannot perform more than one determinations in 40 mL of ethanol (with 0. too high titer). You cannot perform more than three determinations in 40 mL of methanol (with 0. You must perform the determination in pure methanol! Less soluble. 30% too high.045 g di-sodium tartrate).METTLER TOLEDO Good Titration PracticeTM in KF Titration Solubility of di-sodium tartrate dihydrate Di-sodium tartrate dihydrate must be completely dissolved (clear solution!) to obtain correct results. Thus. Procedure To achieve an optimum consumption of 2 to 3 mL titrant with a concentration of 5 mg/mL.g. In Solvent*/chloroform mixture 1:1 or Solvent*/decanol mixture 1:1 In Solvent*/formamide mixture 1:1 In methanol In methanol/chloroform mixture 1:1 or methanol/decanol mixture 1:1 In methanol/formamide mixture 1:1 In solvent for aldehydes and ketones (one-component reagent) In ethanol *Solvent: solvent for the two-component reagent 4. "HYDRANAL®-Water Standard 10.0. 35 . You can only perform one determination in 50 mL of 1:1 mixture (with 0.05 g di-sodium tartrate dihydrate). You can perform eight determinations in 40 mL of this mixture before you need to change the solvent.3 Concentration determination with Water Standard 10. mixing time 2 to 3 minutes. The water standards are supplied in glass ampoules. Highly soluble.0 to 1. Partially soluble. mixing time 1 minute.0" from Sigma-Aldrich® with 10 mg water in 10 g standard. you should weigh in 1. Partially soluble.e. The values obtained are approximately 10% too high. A cloudy solution will falsify the results (i. You can perform six determinations in 30 mL of Solvent* before you need to change it. The values that are obtained are approx. e.3. always take into account the limited solubility of di-sodium tartrate dihydrate in the most commonly used solvents for Karl Fischer titrations: In Solvent* Highly soluble. This content is confirmed by the test certificate enclosed with every package. They are thus protected against the ingress of moisture and can be stored for up to five years.05 g di-sodium tartrate). You must either change the solvent after every sample or use pure Solvent* for the determination.

Glass syringes are better. A balance with a resolution of 0. Determine the weight by back weighing. – – – 36 . a very good deal of practice and precise working is required to obtain repeatable.0 µL deionized water with a 10 µL syringe.4 Concentration determination with pure water General When using pure water to determine the concentration. 6. or with a 10. Open the ampoule shortly before the measurement in accordance with the enclosed instructions. 2.0 mg water/g for a titrant concentration of 2 or 1 mg/mL. the whole content of the ampoule is completely drawn into the syringe.01 mg (e. Inject exactly 10. 4.METTLER TOLEDO Good Titration PracticeTM in KF Titration – – – – – – Notes 1. Use a new ampoule for each new concentration determination.0 mg/g water standard.3.01 g as the sample size. Rinse a 10 mL syringe with approximately 1 mL of water standard. accurate results. 3. the water content is increased and thus this will falsify the results. The content of an ampoule is sufficient for 3 to 5 determinations. Use the METTLER TOLEDO method M300 The water standard is highly soluble in all commonly used solvents for Karl Fischer titration and can therefore be used without restrictions.g. You can use a water standard with 1. The sample should be weighed either using a balance with a resolution of 0. Thus.5 mL at a time as an aliquot. it is strongly recommended determining the concentration either with di-sodium tartrate dihydrate. Enter 0. with a Hamilton microliter syringe). Inject 1 to 1. 5. Plastic syringes may introduce a small amount of moisture. 4. In an open ampoule the liquid standard is exposed to air moisture.g. Start the titration without any mixing time. Draw the whole content of the ampoule into the 10 mL syringe. Procedure – – You should weigh between 10 and 20 µL of deionized water or water according to ISO 3696 to achieve a consumption of 2 to 4 mL titrant with a concentration of 5 mg/mL. The error is minimized by rinsing and conditioning the syringe beforehand. This is due to the very small amount of sample (10 to 20 µL) that has to be injected. To reduce the influence of the atmospheric moisture. METTLER TOLEDO XP205 balance) or with a 10 or 20 µL precision syringe (e.1 mg does not satisfy the requirements for a repeatable titration. Start the titration without any mixing time.

kerosene Pharmaceutical products: ointments. salicylic acid Foods: honey. All the screws in the syringe must be tightened securely. It is possible to determine the titrant concentration with water in all the solvents commonly used for Karl Fischer titration. ester Organic products: urea.METTLER TOLEDO Good Titration PracticeTM in KF Titration Notes 1. beverages Cosmetics: soaps.5 The solvent To determine the water content in a sample. yogurt.0 µL. After setting the volume. You can use mixture of solvents to achieve complete dissolution. Always use a syringe with a long metal shaft. massage oil. emulsions Petrochemical products: crude oil. fat Oils: edible oil. potato chips Chloroform Decanol Octanol Hexanol Dodecanol Toluene Formamide 70% 50% 50% 50% (30%) 37 . Hold the syringe at right angles directly in front of your eyes to read off the value. tar products. noodles. the largest part of the solvent mixture must always be an alcohol (most preferably methanol) to ensure that the Karl Fischer reaction is strictly stoichiometric. caramel. You can get rid of any bubbles in the syringe by expelling the water rapidly. dioxane. suppositories Sugar products: jelly. transformer oil. diesel oil. amount 100% Samples Solvents: toluene. Adjust the plunger to exactly 10. ethereal oils Petrochemical products: gasoline. Only freely available water undergoes reaction with the Karl Fischer reagent. lay it down on the adapter and empty it completely. alcohols. corn. You should always observe the following points when determining the concentration with a 10 µL syringe: Precondition the 10 µL syringe for approximately one hour by filling it with water. jelly bears Starch products: flour. Insert the syringe through the 1 mm hole of the three-hole adapter. if it is absorbent. Always add each sample in exactly the same way.3. hydraulic oil. the sample must release water completely. wipe off any drops that have adhered to the needle with two fingers (be careful if you use a paper towel. 2. However. fatty creams Waxes. Do not warm the syringe. it may draw water out of the needle!). to avoid touching the glass part. Solvent Methanol Max. creams. - 4.

the water will no longer be completely released.3. Sugar is the only type of sample that dissolves in formamide. or by indicating the maximum number of samples to be titrated. 2. 50°C). The extraction capacity can be improved by increasing the temperature (e. This will lead to incorrect results. Once again. The amount of formamide at 50 °C should not exceed 30%. buffering agents are first added to the solvent to ensure that the titration is quick and without side reactions: .6 Dissolving capacity of the solvent The dissolving or extraction capacity of the solvent is a crucial factor in Karl Fischer titration. and .g. The titrator accumulates the total water amount continuously during titrations and reports "Solvent capacity exhausted" as soon as the specified value is exceeded. 3. too low water content. or the titration will take too long and titrant will be wasted. formamide effectively extracts water from starch products. the titration of subsequent samples will then be very slow. 4.e. it is necessary to replace the solvent timely. i. starch products will not dissolve in it. The solvents that are used should contain as few water as possible (< 100 ppm). The Compact Line KF titrators are able to monitor the solvent capacity: the user can define when the solvent should be replaced by specifying the usable life. If acidic or basic samples are titrated. 38 .salicylic or benzoic acid for basic samples. you must replace the solvent timely. which may be completely expended if you titrate a large number of samples with high water content. Therefore. If exhausted.METTLER TOLEDO Good Titration PracticeTM in KF Titration Notes 1. the amount of water in mg which has been titrated. The solvent for the two-component reagent contains SO2. or the stoichiometry of the Karl Fischer reaction will change and the results will be wrong. In this case.imidazole is used for acidic samples. On the other hand.

3. 4. you should determine its water content as soon as possible. oils. Heterogeneous water distribution in samples: In non-polar liquids.g. keep it in a tightly sealed bottle: Glass bottles are preferable to plastic bottles because plastic is not completely gastight. the water is not uniformly dispersed. The sample must be representative. In such cases. The sample should be taken quickly to exclude. Use bottles with a septum stopper for liquids of very low water content. In the case of non-polar solids. With liquid samples that do not dissolve water such as oils. and thus air moisture can penetrate the plastic and absorbed by the sample. "An analysis cannot be better than the actual sample!" When sampling. e. Use sample bottles with small openings to minimize the ingress of moisture. Liquids of this type must be thoroughly mixed (by shaking) before a sample is taken. the absorption or release of moisture. the solubility of water in the sample can be increased using a solubility promotion agent such as 2-propanol.e. or at least minimize. you must be extremely careful to exclude atmospheric moisture . which cannot be mixed as thoroughly as liquids. The sample must therefore be taken very quickly and with a syringe or a spatula that is absolutely dry. i. water may be separated from the sample if it is left to stand for a long time. 5. such as butter. Use a bottle with an optimum volume for the amount of sample: the smaller the gas space above the sample. With liquid samples. 2. Hygroscopic solids may exhibit higher water content on the surface than inside if they have absorbed atmospheric moisture during storage. Substances with very low water content: Substances with a very low water content are frequently extremely hygroscopic. If the water content of a sample changes during sampling due to moisture being absorbed or desorbed. 5. It floats on the surface or sinks to the bottom. 39 .1 Taking the sample When taking samples for water determination. the lower the amount of moisture. If you have to store the sample. you will no longer be able to determine its true water content. rinse the bottles two or three times with the sample beforehand.2 Storing the sample After you have taken the sample. you should take into account the following points: 1. This can happen when a sample cools and the water solubility is decreased. it must contain the same average amount of water as the material as a whole. the sample should be larger the more heterogeneous the distribution of the water.METTLER TOLEDO Good Titration PracticeTM in KF Titration 5 Sampling 5.the most common source of error.

0 1000 1 1. This corresponds to 7. In general.2 1.3 Amount of sample The amount of sample used depends on • • the expected water content. the accuracy is improved if larger sample amounts are used.05 mg water per sample with a titrant concentration of 1 mg/mL.METTLER TOLEDO Good Titration PracticeTM in KF Titration 5.1 1.1 to 0. sample size [ppm] [g] 10 8 50 7 100 5 200 4 500 3 1000 2 40 .4 500 2 1. Repeatable results can be obtained even with 0. and the required accuracy and precision.01 10 8 0. approx.05 mL is thus still acceptable when using a 5 mL burette.0 For volumetric titrations.1 mg water per sample. As a rule of thumb.5 to 17.5 mg water per sample for a 5 mL burette with a titrant concentration of 5 mg/mL. the accuracy increases with the amount of sample. a KF titrant with a lower concentration (1 or 2 mg/mL) has to be used.0 10000 = 1% 0.0 5000 0. it is recommended to use the minimum sample size given in the following table: Water content Min.08 50 5 0. For coulometric analyses. because the absorption of air moisture during sampling and sample addition becomes less important. A titrant consumption of 0. the optimum amount of water is in the range from 0. 10-50 μg water can be detected if the demand for repeatability is not too high. For a more accurate determination of water traces (10 ppm to 1000 ppm) by volumetric KF ttiration. Under optimum measurement conditions. the optimum amount of water is approximately 10 mg per sample. the amount of sample should require a titrant consumption between 30 and 70% of the nominal burette volume. because the absorption of atmospheric moisture during sampling or sample addition becomes less important.1 to 0. and the following minimum sample sizes should be used: Water content Min. sample size Amount of water [ppm] [g] [mg] 1 10 0. For optimum accuracy with determinations in the range from 1 ppm to 1% water.25 100 4 0. If a high level of accuracy is required. Water content determinations below 1000 ppm are not required to be quite as accurate: a relative standard deviation srel of 1 to 5% is generally considered as acceptable for such values. This corresponds to 0.5 to 2 mg water per sample.

The intersection point of this line with the "Amount of sample" scale represents the recommended amount of sample to be used. Procedure: • • • Note: Start from the optimum point (10 mg for volumetric KF. Logarithmic scale! 41 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Determination of the amount of sample for a water content in the range from 1000 ppm to 100% Principle: The recommended sample size can be determined as a function of the expected water content for optimum KF analysis. 1 mg for coulometric KF) or the recommended range The optimum point is connected by a straight line to the expected water content.

which is accessible in the online titrations screen: Dependent on the expected water content. 42 . an optimum sample weight range is recommended.METTLER TOLEDO Good Titration PracticeTM in KF Titration Example: Expected water content: Optimum amount of water: Optimum sample amount: 5000 ppm 10 mg/sample 2g The Compact volumetric and colometric KF titrators support the user with a sample size calculation routine.

Inject it into the cell using a wide-bore needle. you can use a syringe without needle since the sample can be added via the larger hole of the three-hole adapter. Store the sample in a bottle with a septum stopper to avoid moisture absorption from the air. aqueous emulsions. In the case of a volumetric Karl Fischer titrator. creams. edible oils hexane. alcoholic beverages methanol. honey a Waxy candle wax. 43 .1 Liquid samples When adding liquid samples. you must take suitable precautions to prevent atmospheric moisture from being absorbed. mineral oils massage oil Procedure Inject the sample into the titration vessel either through a septum (KF coulometer) or through the needle hole in the three-hole adapter (volumetric KF titrator) using a 1 mL syringe with needle. yoghurt. 50 °C and fill it into a syringe. In the case of a volumetric Karl Fischer titrator. The syringe is heated together with the wax.METTLER TOLEDO Good Titration PracticeTM in KF Titration 6 Sample addition 6. especially with samples of low water content. benzene glycerol. hydraulic oils. suppositories b c Liquefy the sample in an oven at approx. This prevents the sample from solidifying in the syringe during the weighing. paraffin. you can use a syringe without needle since the sample can be added via the larger hole of the three-hole adapter. The following procedures are suitable for the different types of liquid samples: Sample characteristics High water content Low viscosity Examples perfumes. Low water content Low water content Hygroscopic Viscous Very viscous ointments. Possibly warm the sample slightly to lower the viscosity. Fill the 5 or 10 mL syringe with sample after removal of the piston. ski wax. toluene. Inject the sample using a 5 or 10 mL syringe with a thick needle into the titration cell. Rinse a 10 mL syringe 2-3 times with the sample Inject the sample using a 1 mL or 10 mL syringe through a septum cap. silicone oil.

Start the titration. Enter the sample size in the titrator or transfer it automatically. Replace the syringe with the remaining sample on the balance and back weigh it. To avoid this. Fill the syringe with sample and wipe the needle with a paper tissue. Sample addition of liquids with the back weighing technique – Fill the syringe to a quarter with sample. Place the syringe (upside down) in a beaker on the balance pan and tare the balance to "0". a vacuum develops in the bottle with septum stopper and it will no longer be possible to take a sample aliquot. Otherwise when the syringe is removed. Empty the syringe (into the waste bottle) and repeat the rinsing two or three times. Withdraw the plunger so that the drop at the tip of the needle is sucked back into the needle. Fill a syringe without a plunger with molecular sieves. use bottles with a septum stopper and pressure equalization. Air flows through the molecular sieve into the bottle when you take a sample aliquot. – – – – – – – – – – 44 . the drop will adhere to the septum. seal it with cotton wool and insert it into the septum bottle using a short needle. Start the titration method by pressing the <Start> button Inject the sample into the titration cell through the septum stopper. Withdraw the plunger and rinse the syringe with the sample by shaking it. If the sample is hygroscopic or has a low water content (< 1000 ppm).METTLER TOLEDO Good Titration PracticeTM in KF Titration Taking samples from a bottle with septum stopper After several samples have been taken. you must aerate the bottle with dry air (equalize the pressure).

jelly bears. Hard. salicylic acid.g. this would lead to an error of 5% to 10%. For instance.g. it is necessary to warm up such samples to room temperature in a closed vessel before weighing. e.g. fatty e. in a volumetric KF titrator solids can be directly transferred into the titration vessel. coarse-grained samples in a closed. almond paste: Cut into small pieces with scissors or a knife and add the sample with a spatula. other methods have to be used for the determination of low water content by KF coulometry in solid samples: • • • External extraction External dissolution Drying oven On the other hand. about 50-100 μg water enter the anode compartment. The sample should be quickly weighed and added to minimize air exposure. jellied fruits. – Add the sample with a weighing boat. Finely powdered Dusty Finely powdered with very low water content Soft – Use a weighing boat with an attached flexible tubing to add the sample: it prevents the sample from adhering to the wall of the titration vessel or to the electrode.2 Solid samples It is not possible to directly titrate solid samples using KF coulometry . 45 . thus. Sample characteristic Brittle Hard/soft Pourable Procedure e. solid fat: – Grate the product and add the sample with a spatula.when the titration cell is opened to add the sample. the storage of samples in a refrigerator may cause water to condense. crystalline samples: Weighing boat – Grind hard. With an optimum sample size of 1 mg water/sample. e. If possible. cellulose powder: – Either weigh the sample in a dry box or extract it externally.g. chocolate. salts. For this reason. pulverize less hard samples in a mortar. cooled analytical mill.METTLER TOLEDO Good Titration PracticeTM in KF Titration 6. depending on the ambient humidity. it should be added under the same conditions as it was transported and stored.

Add the sample into the titration vessel. Do not use a syringe. chocolate cream. to prevent the sample from adhering to the vessel wall or to the electrode. Tare the balance to zero. butter.g. sugar products – The METTLER TOLEDO Visco-Spoon™ simplifies the handling with creamy samples since it can be directly mounted into the titration stand. Back-weigh the empty weighing boat. paraffin. honey. Enter the weight in the titrator or transfer it automatically. The syringe is heated up together with the wax.METTLER TOLEDO Good Titration PracticeTM in KF Titration Soft.g. Use a weighing boat with attached flexible tubing if necessary. 50 °C and fill them into a syringe. This prevents the sample from hardening inside the syringe during the weighing process Creamy Highly viscous e. Start the titration. candles. margarine. inhomogeneous e.g. – Add the sample with a spatula. because the water is released if it is pressurized Waxy e. Weight of solid samples with the back-weighing technique Weigh the sample in the weighing boat. suppositories: – Liquefy the samples in a drying oven at approx. edible fat: – Homogenize the sample well: the water is heterogeneously distributed. ski wax. - 46 . The water content is often lower atthe surface than inside the sample. fatty.

dried fruit and vegetables.g. organic salts. e.g. crystalline products: Pulverize in a mortar.g. pharmaceuticals Water Example: Food Example: Gypsum (Ca2SO4 * 2 H2O) Thus. berries: Reduce with a homogenizer in an external solvent. e. brittle Moderately hard. coffee beans: Crush in a mixer.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7 Release of water from the sample Karl Fischer titration is only possible if the water in the samples is freely available.g. solid fat: Grate the product.g.g. then reduce it further with a homogenizer in an external solvent.g. e. fatty Mince the product. sausage. fatty Soft. hard salts: Grind in a closed. chocolate. vegetable juices: Reduce with a homogenizer. cooled analytical mill. inorganic salts. Fibrous natural products Suspensions 47 .g. e. fruit juice extracts. e.g. jellied fruits. suitable sample preparations and special Karl Fischer methods are necessary to release water in these samples. it is necessary to crush insoluble solids in order to gain access to the trapped water.g. almond paste (“marzipan”): Cut into small pieces with scissors or a knife. in plants) Water Example: Sugar. e. grain. water adsorbed on surface capillary bounded water (e.: • • • • entrapped water water of crystallization (salts). The following methods are available: Sample characteristic Very hard Procedure e. meat. minerals. noodles. Sample preparation Water: Example: Biological samples First of all. brittle Viscous Hard. e. This is not the case with solids if the water is bound as. e. cheese: Hard.

0 7. hazelnuts.9 0.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. potato chips.g.8 1. etc.2 1.5 1.9 0. using either methanol or a mixture of it as the solvent.4 0. Water is then extracted providing the mixing time defined in the titration method is sufficiently long.4 1.1 4. e.4 1.3 2.8 1.9 srel / % 0. heating the solution with a thermostating titration beaker. sugar.1 1.8 Solvent Formamide:methanol 2:3 at 50 °C Formamide:methanol 2:3 at 50 °C Formamide:methanol 2:3 at 50 °C Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol 48 . grinding the sample additionally with a built-in homogenizer (see photos below).1 Internal extraction Internal extraction is suitable for insoluble solids that release water quickly when crushed: – – Add the crushed samples into the titration vessel. the homogenizer eliminates the need to use auxiliary reagents such as formamide with.5 8. You can speed up the extraction of water from the sample by • • In many cases.0 1. Thermostatable vessel High–speed homogenizer Examples: Sample Flour Potato chips Ground hazelnuts Chocolate Instant coffee Dried chives Dried tarragon Aspirin Sweetener tablets Optical bleaching agent Result / % 12.3 1.1 mg/pc 3.8 4.

edible fat) for natural substances (almonds. 49 . pepper. the finely crushed sample is added to a solvent with very low water content and is left to stand until the water has been released from the sample. water is extracted from the sample by means of a defined quantity of solvent of known water content. In particular. Pay attention to the water capacity of chloroform (max. butter milk. methanol decanol / octanol formamide for insoluble organic solids for fatty and dairy products (butter. sugar and starch products for sugar (surface water) The organic solvents most commonly used are: • chloroform The external extraction is carried out in four steps: Step 1: Blank value determination of the extraction solvent Solvent in septum bottle Take a solvent aliquot Water content determination of solvent = blank value B - The water content of the solvent must be much less than the one of the sample. The extraction of water can be improved • • • by shaking the solution (mechanical shaker. Provide sufficient solvent for the blank value determination so that enough solvent is available for the extraction. shaking bath) placing the solution in an ultrasonic bath for a certain time or reducing the sample further with a built-in homogenizer. 600 ppm). Briefly. curry) for dehydrated products for sugar (total water).METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. 350 ppm) and toluene (max.2 External extraction External extraction is suitable for insoluble solids that release water only slowly when crushed as well as for samples with an extremely inhomogeneous water distribution.

Add a sufficient amount of sample. or use a homogenizer. Step 3: Extraction - Shake. For the extraction of tablets. The larger the sample. A dilution factor of 10 . A mechanical shaker is normally used because the extraction time is often long (at least two hours or overnight). the smaller the relative error because the total error is calculated with respect to the sample size. the addition of dry quartz sand has proven useful for improving and speeding up the extraction. Shaking is the method generally used for extraction. - 50 . or use an ultrasonic bath with heating.20 is normally used.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 2: Weigh in solvent and sample Weigh solvent in = msolv Add sample Weigh sample = mext - Cut the sample into small pieces so that it releases its water more quickly and efficiently.

% or ppm).1/m ppm: C = (VEQ*CONC-TIME*DRIFT/1000)*1000/m . 51 . Water content of the supernatant extraction solvent (% or ppm) %: C = (VEQ*CONC-TIME*DRIFT/1000)*0. R: C: B: msol: mext: m: Note: Blank value (water content of the solvent. take an aliquot and titrate Allow to settle Take an aliquot of the extraction solution Titrate sample The following equations are used to calculate the water content of the extracted sample: ⎛ msol B ⋅ msol ⋅ ⎜C ⋅ − ⎜ mext mext ⎝ ⎞ ⎟ ⎟ ⎠ For % : R (%) = 100 100 − C For ppm : 10 6 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − R( ppm) = 6 ⎟ mext ⎠ 10 − C ⎝ mext Water content in the sample P (% or ppm).METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 4: Allow settling. Amount of solvent (g) Amount of sample (g) extracted with the solvent Weight of the sample aliquot (g) The detailed calculations which lead to these formulas are given in the appendix.

the weight of the sample (mext) and the weight of the aliquot of the supernatant solution containing the extracted water (sample size m) is entered into the respective sample data fields: 52 .4 0. The METTLER TOLEDO methods M305 for the volumetric KF titrator and M394 for the coulometric KF titrator are available with optimized method parameters for immediate execution.6 0.9 11. The solvent blank is determined directly from the method running in standby by pressing the ‘Start blank’ button.5 9.2 Chloroform Volumetric KF Titration Sample Result / % srel / % Extraction solvent Cheese Liver sausage Mustard Chicken broth Tobacco Wool Acrylic paint 27.4 0.5 0.4 4.3 0.3 0.4 0. The weight of the solvent (msol).METTLER TOLEDO Good Titration PracticeTM in KF Titration Examples for the external extraction: KF Coulometry Sample Result / ppm srel / % Extraction solvent Sucrose (surface water) 72 4.6 61.6 72.8 54.5 Decanol:formamide:methanol 8:2:1 Decanol:formamide:methanol 8:2:1 Decanol:formamide 1:1 Decanol:formamide:methanol 8:2:1 Methanol Methanol Formamide There is a dedicated KF method type ‘External Extraction’.

The amount of sample should also take account of the absorption capacity of the solvent.e. the formula is automatically given. reaches the saturation limit for water already at 350 ppm! 53 . “External extraction”) in the method function “Calculation”. for instance. The water content of the solvent should be as low as possible. in order to maximize the extraction effect and ensure that the difference between the water contents before and after extraction is as large as possible.METTLER TOLEDO Good Titration PracticeTM in KF Titration The equation for the calculation of the water content of the extracted sample is predefined in the calculation method function. Chloroform. The amount of sample should be sufficiently large to ensure that the amount of water in the sample is significantly greater than that in the solvent prior to extraction. 3. by selecting the appropriate calculation (i. Note: 1. 2. In particular.

1/m ppm: C = (VEQ*CONC-TIME*DRIFT/1000)*1000/m B: msol: mext: m: Blank value (water content in % or ppm) of the solvent.8 2. waxes and suppositories Example: Sample Result / ppm srel / % External solvent Sucrose (total water) Naphthalene Phenol Salicylic acid Contact adhesive (“Rubber cement”) 533 35 174 116 278 4.3 formamide methanol methanol methanol chloroform The method corresponds to external extraction except that the sample dissolves completely in the external solvent. %: C = (VEQ*CONC-TIME*DRIFT/1000)*0. in % or ppm.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. or with a very low water content.9 5. the addition of methanol is not necessary.2 10. only the calculation method function has to be adapted to by selecting the corresponding calculation from the list of proposed results. ppm ) = C ⋅ ⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ For % AND ppm: R: C: Water content in the sample P (% or ppm) Total water content (sample + solvent). ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R(%. The following solvents are commonly used: • • • • methanol formamide chloroform toluene for organic solids for sugar products for petroleum oils and adhesives for tar. or with a high water content Pure solvents can be used to dissolve the samples. External dissolution is suitable for soluble solids with an extremely inhomogeneous water distribution.2 1.3 External dissolution External dissolution is defined as the complete dissolution of a sample in a defined amount of solvent of known water content. The dedicated method type ‘External Extraction’ and the METTLER TOLEDO methods M305 for the volumetric KF titrator and M394 for the coulometric KF titrator can be used as templates. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent Weight of the sample aliquot (g) 54 .

Direct titration is not suitable. In fact. You should therefore proceed as it follows: Take an aliquot of anolyte Inject it in the septum bottle Shake Take aliquot and titrate Procedure: 1. Rinse the syringe two or three times in this way. this error is reduced. Thus. weigh it and inject it into the titration cell. because a large sample amount leads to a too long titration time. Shake the bottle or place it in an ultrasonic bath for 5 minutes so that the lyophilized substance dissolves or forms a suspension. Draw 10 . 7. the error as a result of opening the titration stand will be between 10 and 30 µg. the blank value correction is too large compared to the amount of water in the sample. and too much titrant is consumed. If the solid has a low water content (<200 ppm). 7. If 1 g of sample has a water content of 100 ppm (= 100 µg) for instance.20 mL of anolyte titrated to dryness into the syringe. Remove approx. foodstuffs) in septum bottles means that external extraction or external dissolution as described in the previous sections are not recommended. KF coulometry is not suitable for samples with water contents of 10-100% because a very small amount of sample would have to be used. weigh it and inject it into the septum bottle. the sample is previously diluted through external dissolution to be able to titrate a larger sample aliquot. 4. 2. On the other hand. Determine the weight by back weighing. 55 . biological tissue. Draw an aliquot into the same syringe again.4 Lyophilized substance in septum bottles The extremely low water content of freeze-dried substances (e. 6. 5. Since you are able to work with larger amounts of sample when working with this technique. 3.METTLER TOLEDO Good Titration PracticeTM in KF Titration To obtain accurate results a large sample amount is used for substances with an inhomogeneous water distribution. serum. Determine the weight of anolyte injected by back weighing. 10 mL of anolyte titrated to dryness from the titration cell using a 20 mL syringe with a long needle and then return it to the titration cell.g. the error obtained by direct titration if the titration stand is opened to add the sample is too large.

3. With a standard method calculation and calculate the water amount in µg. Alternative procedure: 1. The water amount in µg is determined. In this way. 10 mL of anolyte titrated to dryness from the titration cell using a 20 mL syringe with a long needle and then return it to the titration cell. Rinse the syringe two or three times in this way. Since ¼ of the total amount was injected. 8. 2. 6. then you can additionally calculate the result can be given in ppm. Remove approx. because the anolyte titrated to dryness has a blank value of "0". Shake the bottle or place it in an ultrasonic bath for 5 minutes so that the lyophilized substance dissolves or forms a suspension. The accuracy of a plastic syringe is enough. If you know the lyophilized sample amount in the septum bottle. Thus. Draw exactly 20 mL of anolyte titrated to dryness into the syringe and inject it into the septum bottle. neither the calculation for the external extraction nor for the external dissolution are needed for this procedure using the volume instead of the mass. the water amount in the septum bottle is 4 times larger. 4. 7. the final result must be multiplied by 4 (factor f = 4). 56 . Draw exactly 5 mL from the septum bottle into the same syringe again and inject it into the titration cell. zero must be entered for the blank value (B).METTLER TOLEDO Good Titration PracticeTM in KF Titration If the sample is completely dissolved: use the method type “External extraction” and the calculation for the "External dissolution" If a suspension is formed: use the method type “External Extraction” and the calculation for the "External extraction" Note: In both cases. 5.

Calculate the volume from the time and the gas flow rate. the gas must be directed through the titration vessel for a defined period of time.If possible. . you must fill the gas either into special gas sample tubes or into small steel cylinders.Purge the sample vessel and the tubings thoroughly beforehand with the gas.When titrating large quantities of gas in the same solvent. Three-way valve Flow meter Gas Control valve The flow rate has to be constant to determine the volume necessary to calculate the water content: gas volume = gas flow rate x time. you should titrate the gas sample directly from the source. time" and a "Delay time" of e. The water content in ppm is calculated by entering the volume and the density. 57 .Add a sufficient amount of buffer solution into the titration vessel to determine the water content of acid gases such as e. 600 s as termination parameters.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. The gas must be directed through a water-dissolving.g. .Stop the gas flow after 1 to 2 mL titrant has been consumed. Sampling/sample addition . If not. .Select "Max. to ensure that the titration is terminated after the maximum time. The water contained in the gas is then absorbed by the liquid and can be determined by means of Karl Fischer titration in a process similar to external extraction.Turn the three-way valve. . .As soon as the drift is stable again. . Notes . .CO2 gas can not be titrated directly since iodine reacts with CO2. .Adjust the gas stream to a constant flow rate with the control valve: 50 to 200 mL/min. . start the titration and reset the three-way valve to its original position in order to direct the gas into the titration vessel.g. hydrochloric acid. evaporated methanol lost in the gas stream must be replaced depending on titration time and number of determinations. depending on the water content of the gas. water-free absorption liquid in which CO2 itself does not dissolve. .Purge the system with the gas before you start the determination. Determination .With sample vessels the gas amount gas can be determined by differential weighing. to prevent the gas from flowing into the titration vessel.5 Determination of water in gases To determine the water content of gases.

7 500 97. which could react with the sample at higher temperatures.1 bar (cf. 11 mg/L nitrogen gas from a cylinder: 1. inorganic samples. for accurate results do not select a too high gas flow rate. 150 mL/min is ideal for DO308 and 70 mL/min for Stromboli (automated KF drying oven. the oven temperature should not exceed 160 °C. chapter 7.1 - The recovery rate is clearly decreasing with increasing gas flow rate.6 Determination using the drying oven This method is suitable for solids and liquids that 1. the residual moisture in the purge gas should be less than at least 10 μg/L (for coulometric determination) and 20 μg/L (for volumetric KF titration) in order to obtain accurate and repeatable results.5 . or 2. For Karl Fischer titration. 7.1 Principle The sample is heated in an oven.4 – 8. The water is transferred to the titration cell in a current of dry inert gas (purge gas).METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. e. and the amount of water is determined. chapter 7. cf. The purge gases commonly used contain moisture.6. 58 .0 mg/L Therefore.5). If you use nitrogen from a gas cylinder. 7.6.g.6. causing the water in the sample to vaporize. cause side reactions with the Karl Fischer reagent. you should use a two-stage pressure regulator so that the final pressure is in the range 0.4) A gas stream of approx. Air should therefore only be used for non-oxidizable. Thus.9 166 99. If you use air for organic samples.6. that release water very slowly. the purge gases must be first dried before entering the KF oven. Experiments with various gas flow rates yielded the following results: Gas flow rate Recovery [mL/min]: [%]: 108 99.2 Purge gas Air contains oxygen.: o o air with 50% humidity: approx.

60 s).50 µg H2O/L 15 – 20 µg H2O/L 50 – 60 µg H2O/L 5 – 10 µg H2O/L 10 – 15 µg H2O/min 8 – 10 µg H2O/min 3 – 4 µg H2O/min 10 – 12 µg H2O/min 1 – 2 µg H2O/min You can use the following desiccants to dry the purge gas: – – Molecular sieves are the best drying agent as far as residual moisture is concerned. The short mix time is necessary so that a delayed vaporization of water does not lead to premature termination of the titration. they are rapidly exhausted.METTLER TOLEDO Good Titration PracticeTM in KF Titration Several agents are available to dry the purge gas: Method Residual moisture Residual moisture for 200 mL/min gas flow rate (drift) Sulfuric acid.6. deactivate the drift stop). especially methanol. Method 1: The water evolved is continuously titrated After a short mix time (20 .e. the titration starts and the released water is continuously titrated. This is caused by a slow release of the final traces of water or slow thermal decomposition of the sample. It is therefore recommended to dry the gas with a combination of silica gel and molecular sieves.3 Procedure There are two different methods to perform a KF titration with the drying oven: 1. With some samples the drift at the end of the titration is significantly higher than the initial drift. Silica gel and molecular sieves have the advantage that they can be regenerated. The amount depends on the gas flow rate and the type of KF reagent present in the titration cell. deactivate the drift stop). Silica gel is appreciably better in this respect. In such cases you should use the maximum titration time as termination parameter (i.e. 2.80 µg H2O/L 40 . To ensure that the determination is repeatable. P2O5 KF one-component reagent Silica gel Molecular sieves 3 Å 50 . whereas molecular sieves requires temperatures up to 300 °C. i. In the case of KF coulometers. The KF titration is then started. Passing the gas stream into the titration cell causes the anolyte (in the KF coulometer) and solvent (generally methanol in KF volumetric titrator) to vaporize. The relative drift stop or the maximum titration time can be used as the termination criterion. in contrast to other desiccants. At the end of the titration. 100% Phosphorous pentoxide. Start off with the silica gel to absorb the bulk of the water and then use molecular sieves to reduce the residual moisture to a minimum. you should set the maximum titration time as the termination parameter (i. the vaporization is often very irregular. 7. Silica gel can be regenerated over night at 150 °C. Method 2: The water is first vaporized and then titrated afterward During a defined long mix time. In order to avoid the latter you may also use the minimum time as termination parameter. but their water absorption capacity is low. all the water is vaporized and transferred to the titration cell. there are two types of anolyte solutions: 59 .e.

of samples srel / % T /°C Time/min Comments Polyamide Polyethylene Motor oil Cement Cooking salt Carbon black 5547 68 842 8200 360 3583 6 6 6 6 5 5 0.9 2.7 99.2 4.g. as well as a gas flow meter. time Max.9 9. 1 mL/hour – From time to time. time Max.1 Briefly: The less methanol is vaporized. Coulomat AG Oven): Anolyte loss at 150 .e.6. As an example data from coulometric determinations are indicated here below: Method Anolyte Gas flow rate Recovery / % 1 1 2 2 Coulomat AG Coulomat AG Oven Coulomat AG Coulomat AG Oven 166 mL/min 183 mL/min 166 mL/min 106 mL/min 99. Make sure that the level of the anolyte does not fall below that of the catholyte (higher drift!). the faster the water is titrated.4 Manual Karl Fischer drying oven The METTLER TOLEDO DO308 drying oven can be operated in a temperature range from 50 to 300 °C. The procedure for the determination of water content is described in the operating instructions. i. 3.e.2 1. and the better the recovery. time Max.95 98.g.5 . time Max. The recovery therefore depends on the amount of methanol vaporized and the method used. oven temperature 200 °C: approx. Examples: Sample Result / ppm No. It has a large glass sample boat capable of holding up to 10 cm3 of sample.200 mL/min. there is a small loss of water. dedicated anolyte to be used with a KF Oven (e. fibers) or with samples of low water content. you should replace the anolyte lost through vaporization with new anhydrous methanol. time Max.g. This is particularly important with low-weight samples (e. The DO308 oven is equipped with a gas drying unit with two bottles for silica gel and molecular sieve. Coulomat AG or CombiCoulomat frit): Anolyte loss at 150 . i. oven temperature 200 °C: approx.2 99.METTLER TOLEDO Good Titration PracticeTM in KF Titration – Standard anolyte solutions containing methanol (e. An air pump is available as an optional accessory. 7.5 mL/hour Anolyte containing ethylene glycol.200 mL/min. the recovery is not 100%.8 6.5 190 280 140 300 300 200 15 10 15 20 10 15 Max. time 60 . Due to the vaporization of the methanol.4.

do not select the parameter "Auto start". you should proceed as follows: 7. 61 9. This can happen when the titration is started only after complete evaporation. Experiments using methanol as the solvent gave a recovery rate of 98% for a stream of 166 mL/min. Then. Close the stop cock and purge the "hot zone". This leads to a too low result. in volumetric KF titration the methanol loss is approx. For the same reason.7%.55% or VWR/VWR/MERCK water standard KF oven 1%. evaporated solvent does not condense in the drying tube. In such cases. 5. 4. 3. bent drying tube. For instance. and/or replace the anolyte of the KF coulometer. you may use the SIGMAALDRICH HYDRANAL® water standard KF oven 5. If the water is titrated as soon as it begins to evaporate. 6. 2. purge the "cold zone". . Always start the titration before you place the sample in the oven to ensure that the correct drift value is adopted by the method (online drift). Some samples require some time before water starts evaporating. If several determinations are performed in the same solvent. the evaporated solvent lost in the gas stream has to be replaced. The drift should be 5-10 μg H2O/min at a gas flow of 150 mL/min. Coulometer KF: The internal drying tube of the generator electrode has to be replaced with an external. and does not drop into the cathode compartment/ titration cell. If the drift is constant. Add the sample through the tapered joint and slide the glass boat with the sample into the oven: Guide rod with magnet Slider Glass sample boat 8. To check the performance of the titrator/drying oven system. replace the silica gel and molecular sieves of the gas drying unit. Set a gas flow rate of 150-200 mL/min. Some samples have surface water that is lost as soon as the oven is purged with dry gas.METTLER TOLEDO Good Titration PracticeTM in KF Titration Comments: 1. the recovery increases to 99.5 to 4 mL/h for an oven temperature of 200 °C and a flow rate of 200 mL/min. 10. The evaporation is reduced by adding ethylene glycol (higher boiling point) to a maximum solvent ratio of 20-30%. Here a short mixing time (15 to 60 s) or the minimum titration time should be defined to prevent the titration from being terminated too early. If the drift is higher than 15 μg H2O/min. 3. start the titration so that the drift value is automatically entered. A large amount of evaporated water cannot be fully absorbed by the solvent. Open the stop cock.

1 During a sample series: 2 3 1. 2.5 STROMBOLI automatic oven sample changer The METTLER TOLEDO STROMBOLI oven sample changer is a drying oven for automatic Karl Fischer titration with the KF Compact Volumetric V30 and Coulometric Tititrators C30 as well as with the Titration Excellence Titrators T70 and T90.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. The oven heats the sample to the set temperature.6. 3. Besides 14 places for glass sample vials. The drying oven can be operated in the temperature range from 50 to 300°C. STROMBOLI offers one fixed place on the sample rack for an empty sample vials in order to determine the drift value. After the analysis. are included in the titration method. while a glass tube pierces the aluminum foil cover. The purge gas flows through the sample vial and the water vaporized is transported via the transfer tube into the titration cell of the coulometer. The sample vials are moved upward into the oven by a lift. STROMBOLI is completely controlled by the titrator: all the parameters for the determination. the lift is moved downward and gravity facilitates the removal of the sample vial from the oven. 62 . including the oven temperature. The blue rubber cap seals the sample vial tightly against the oven.

This is particularly important with light samples (e. To determine the drift value accurately. The sample vials are sealed with self-sealing aluminum foil and a rubber cup. the moisture in the empty sample vial has first to be removed. The drift value is defined as the moisture entered into the titration cell by the purge gas.g. fibers) or with samples of low water content. This takes 10-20 minutes as can be seen in the following diagram: 63 . Drift determination: The drift determination is performed with an empty vial on the first position of the sample rack.METTLER TOLEDO Good Titration PracticeTM in KF Titration Sample vials: Rubber cap Aluminum foil Sample vial The glass sample vials have a large volume (up to 25 mL).

suboptimum conditions. The blank value can also vary as a function of temperature. a blank value determination should be performed before each series of samples since the ambient conditions (humidity. at the end of a series the blank value can be measured again and compared with the value determined at the beginning. several blank value determinations can be performed one after the other in the same loop and the mean value calculated from the results. By performing a drift determination at the end of the series or between several series. for example. whose optimum bake-out temperatures differ.e. There are dedicated METTLER TOLEDO multi-loop methods available in the V30 (M313) and in the C30 (M396).300 μg water.e. The first sample of the next loop is then transferred into the oven and the water determination begins. moisture in the sample vial. the last sample vial that was baked out remains in the oven until the temperature has stabilized at the temperature of the next loop and the drift is low and stable. you can check whether the drift is constant and the new drift value can be used for the next series. > 15 μg H2O/min). This means that the stored drift value of the previous determination will be used. Thus. The optimum blank value is in the range of 70 . These method templates are based on a dedicated KF method type called ‘Stromboli’.the analysis times for the determination of the blank value and for each sample are the same.e. a blank determination can be performed between two sample loops.) are always slightly different. gas flow. The new blank value is automatically used for the blank correction. In this case. drift value x time). it is important to use a new sample vial for each blank value determination (i. the blank value determination also takes the actual drift into account. 64 . the method contains a so-called sample loop.g. For each series. If this is the case. Multiple sample series at different temperatures Several series can be started on the same sample turntable – even at different temperatures. the drift value can change with time. you can enter the number of samples the series includes for each loop. If the temperatures of successive loops are different. Important: After a blank value determination. i. With rapidly changing. different plastic samples have to be analyzed. In the same way. as well as the anolyte in a coulometric analysis.METTLER TOLEDO Good Titration PracticeTM in KF Titration Blank value determination: The blank value is the amount of water contained in an empty sample vial (i. the moisture in the air present in the vial. etc. one with the same properties as the sample vials into which the samples have been filled in). The blank value should be determined before each series because the humidity can change.e. It is therefore not necessary to perform a drift determination before each series. To determine the blank value as accurately as possible. Nevertheless. a drift determination should still be performed at least once a day in order to check whether the drift is too high (e. In this case. the silica gel and molecular sieves in the bottles of the gas drying unit can be replaced. and the adsorbed moisture on the glass walls of the vial) minus the amount of water due to the drift (i. The loops run through one after the other and the samples are processed sample for sample. and thus the moisture adsorbed on the glass walls is not always the same. the moisture content is somewhat lower. they can be measured at different temperatures using the same method. If. the vial used no longer has the same properties as the "fresh" sample vials. If the maximum titration time is used as termination criterion in the method -which is what we recommend. At the start of the method. Performing the drift and blank value determination In general.

A special (longer) gas inlet glass tube is provided to bubble gas into the liquid. 2. These are partially vaporized (e. 4. To check the titrator/drying oven system. you can use SIGMA-ALDRICH HYDRANAL® water standard KF oven 5.g. This test also serves to check the tightness of the oven and the connection tubing 65 . 8. drying and storage).g. that the inert gas stream to the gas source is closed and the system is ventilated with ambient air. Therefore no precious inert gas is lost and no vacuum is applied to the system which may result in a back aspiration of the anolyte into the hot oven. 3. 6. 7. you can not only determine solids but also liquid samples.METTLER TOLEDO Good Titration PracticeTM in KF Titration Comments on the operation with the STROMBOLI oven sample changer: 1. since it provides a leak free inert gas stream during normal operation. This has a large effect on the blank value and thus on the result. Allow sample vials that have been used or cleaned to stand overnight in the atmosphere for conditioning before starting measurements. The amount of moisture adhering to the glass surface of the sample vials strongly depends on how the vials were treated beforehand (cleaning. Use the same vials for a sample series as well as for the blank value determination.55% or VWR/VWR/MERCK water standard KF oven 1%. and therefore it does not drop into the cathode compartment. With STROMBOLI. evaporated solvent is not condensing in the drying tube. An optional 3/2 way valve which is automatically controlled by STROMBOLI can be used instead of the T-piece mentioned in 1. toluene. This is necessary so that the KF solvent or anolyte is not aspirated into the hot sample vial if Stromboli is not properly shut down while it is still hot. Vials that have undergone different treatment can show differences in the blank value of 50-150 μg water. This valve shall be used especially if inert gas sources are used. In this way. motor oil) or completely vaporized (e. Set a gas flow of 40–60 mL/min. The delivery tube has a T-piece that causes a small leak flow. 5. bent drying tube. KF Coulometer C30: The internal drying tube of the generator electrode has to be replaced with an external. A sudden shutdown of power immediately switches the valve in that way. see also list of results).

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

Examples:
Sample Result [ppm] No. of samples srel [%] T [°C]
Max.Time

[s]

Comments

Polylactic acid 0.5 g Polymer ABS-50 T 10014 3g Polymer ABS-50 F10014 2g Motor oil 1120/03 (AA) 2g

2589

3

1.1

160, air 190, N2gas 170, N2gas 165, air

--

Stir time: Max. time: rel. drift:

600 s 300 s 3 µg/min

736

5

1.1

300

Stir time: 900 s Delay time: 300 s Stir time: 900 s Delay time: 300 s Stir time: 60 s Delay time: 300 s Very slow evaporation, not faster with 180°C, above 180°C decomposition Stir time: 60 s Delay time: 300 s Very slow evaporation, above 180°C decomposition

1312

13

0.9

300

241 261

3 4

4.4 7.9

1500

Motor oil 1034/03 (AA) 1.5 g

426 438

4 3

2.7 4.5

180, air

1800

66

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

8 Measurement results
8.1 Resolution and detection limit
The following table indicates the theoretically smallest increments of current (KF coulometric) and titrant (Volumetric KF) which could be achieved by the instruments based on their technical specifications. Therefore, these are indicative values and they should be considered as such:
C20/C30 Compact Coulometric Instrument V20/V30 Compact Volumetric Titrator Resolution: 20’000 burette steps
5 mL burette: 0.25 µL c=5 mg H2O/mL: 1.25 µg H2O/step

Theoretical smallest increment

0.1 mC
Theoretical: Resolution:

(100 mA x 1 ms)
0.01 µg H2O < 0.1 µg H2O

Detection limit (limit of detection, LOD)

10 µg
Example: 10 g sample → determ. of 1 ppm Assumptions: - Current is used for iodine generation - Generated iodine is reacting 100% with water only.

50 x resolution
5 mL burette: 12.5 µL c=5 mg H2O/mL: 62.5 µg H2O Example: 5 g sample → determ. of 12.5 ppm

The theoretically smallest current increment that can be generated by the C20/C30 Compact Coulometers is 0.10712 mC which corresponds to 0.01 μg water. However, the achievable resolution of the instrument is in the order of less than 0.1 µg H2O, whereas the detection limit (also called “limit of detection”) is approx. 10 μg water per sample. Thus with a 10 g sample, 1 ppm water can be determined. For the V20/V30 Compact Volumetric instruments, the detection limit mainly depends on • • • The resolution of the burette drive, i.e. the max. number of steps which can be achieved by the stepper motor. the burette volume size; generally, a 5 mL burette is used for volumetric KF titration. The concentration of the titrant.

8.2 Measurement accuracy
The accuracy strongly depends not only on the technical specifications of the instruments, but also on the several factors that have been already mentioned in the previous chapters: 1. Sampling (including suitable storage, if necessary) 2. Sample treatment and preparation 3. Expected water content and selection of suitable instrument 4. Selection of optimum sample size 5. Condition of the KF reagents, i.e. fresh reagents, pre-titration, low drift value, … 6. Sealed titration vessel and tight tubing, 7. Condition of the indication electrode 8. Coulometry: condition of the generating cell 9. Parameter settings in the titration method etc. 67

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

To determine the closeness of agreement between the result of measurement and the true sample value, measurements can be performed either by titrating water standards or by titrating samples with known water content. The measurement accuracy depends on all the various factors described and explained in the previous sections. The crucial factors are optimum control as well as the water content and the amount of the sample.

8.3 Repeatability
The closeness of the agreement between the results of successive measurements of the same sample can be expressed quantitatively as the relative standard deviation, srel, given as %. With optimum sample amount and control, the following values can be obtained under test conditions for repeatability. The graph shows the relative standard deviation for different water contents. In general, the repeatability of a sample series becomes worse with decreasing water content. Note that for water content below 10 ppm it is not recommended to use a volumetric technique.

100% 10% 1% 1000 ppm 100 ppm 10 ppm 1 ppm

Coulometry
Not suitable for coulometry

Volumetry
srel < 0.5 %

srel < 0.5 %

srel 5 - 0.5 % srel 5 - 0.5 % srel > 5 % srel > 5 %
Not suitable for volumetry

In the following graphs, the relative standard deviation srel (%) of several series with different water content are given as a function of the sample size:

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sample size for different water contents: KF Coulometry KF Volumetric Titration: srel (%) 6 110 ppm 5 330 ppm 4 720 ppm 3 2 1 0 0. 69 .5 1.0 5. Therefore. it is necessary to use the optimum sample size in order to achieve precise results.0 3.25 0. with decreasing sample size the relative standard deviation srel becomes worse.0 2.METTLER TOLEDO Good Titration PracticeTM in KF Titration Relative standard deviation srel vs.0 Sample size (g) In both cases. A good repeatability is achieved the sample size is increased particularly for low water content values.

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

9 Interferences
9.1 Effects of temperature
Temperature effects on the KF titrant The Karl Fischer titrants consist of approximately 90% methanol or ethanol. Their volume increases considerably if the temperature increases, and their concentration decreases accordingly. S. Eberius [3] specifies a correction factor of 0.0012 per degree Celsius for methanolic Karl Fischer solutions. According to ISO 760, a temperature increase of 1 °C causes a drop of 0.1% in the concentration. The titrant (in particular, the two-component KF solvent) may loose sulfur dioxide if the temperature rises. This causes bubbles to form in the titrant tubing, an effect which is worse the faster the rate at which the burette is filled. These titrators allow you to define the filling rate of the burette separately for each titrant, e.g.:
Temperature / °C < 15 15 – 30 > 30

Filling rate for one-component KF volumetric titrant / % Filling rate for two-component KF volumetric titrant / %

100 80

100 60

70 40

Titration at low temperatures You can perform Karl Fischer titrations at low temperature to eliminate undesired side reactions. The water content of peroxides, for example, can be determined at -40 °C. You must use the two-component reagent to do so, because the reaction rate of the onecomponent reagent is too slow at this temperature. Titration at high temperatures Increasing the titration temperature speeds up the dissolution of the sample or the extraction of the water from it, resulting in shorter titration times. Titrations at elevated temperature have proved particularly effective for foodstuffs, e.g. sugar, flour, potato flakes, hazelnuts, custard powder. The maximum temperature depends on the boiling point of the reagent (boiling point of methanol: 64 °C, boiling point of ethanol: 78 °C).

9.2 Side reactions
Side reactions that falsify the results can occur parallel to the Karl Fischer titration. There are mainly three side reactions that can affect the result: 1. Reaction with methanol, CH3OH Aldehydes and ketones react with methanol leading to additional water Esterification with carboxylic acids leading to additional water Ketones and aldehydes react with sulphur dioxide, a base and water (i.e. water is consumed) The reaction of iodine with e.g. oxides, hydroxides, carbonates, amines, ascorbic acid, and mercaptans leads to a higher consumption of iodine giving higher water content.

2. Reaction with water, H2O

3. Reaction with iodine, I2 -

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Good Titration PracticeTM in KF Titration

9.2.1 Reaction with methanol
Aldehydes and ketones: Methanol, CH3OH, reacts with aldehydes (R-CHO) and ketones (R-CO-R) to form acetals (CH3-CH(OR2)2 , and (CH3)2C(OR2)2 respectively, the latter also called ketals), as well as water: Formation of acetals:

CH3CHO + 2 CH3OH
Formation of ketals:

→ →

CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O

(CH3)2CO + 2 CH3OH
Solution: -

Use the special reagents for aldehydes and ketones with these substances (so-called K-reagents). They contain other alcohols than methanol. - Experiments have shown that the side reaction still takes place despite these reagents. Each time acetone is determined, for example, the drift is higher than before the titration: the larger the sample, the greater the drift increase. It is therefore recommend to perform the determination with a small sample amount and to replace the solvent after two or three samples. Esterification: Methanol, CH3OH, reacts under presence of strong acids (i.e. sulfuric acid) with carboxylic acids (R-COOH) to an ester (R-O-CO-CH3) and additional water:

R-COOH + CH3OH →
Solution: -

R-COO-CH3 + H2O

First neutralize the sample using a suitable base (imidazole) before KF titration.

9.2.2 Reaction with water
Another side reaction, the bisulfite addition, occurs with aldehydes and ketones in the presence of SO2. Water is consumed in the process. Bisulfite addition:

CH3CHO + H2O + SO2 + NR R1-CO-R2 + HSO3Note: SO2 + H2O = HSO3- + H+ Solution:

→ →

HC(OH)SO3HNR R1(R2)C(OH)SO3-

- Start the titration immediately after adding the sample. - Perform a fast titration by predispensing 90% of titrant consumption This causes the water to be titrated quickly, before any bisulfite addition can take place. The "Autostart" parameter allows for the automatic start of the titration as soon as the sample has been added and water is detected.

9.3 Reaction with iodine
The Karl Fischer reaction is a REDOX reaction with iodine as the oxidizing agent. Thus, iodine may also react with readily oxidizable samples. On the other hand, iodine can also be reduced by SO2 in some samples such as e.g. oxides. Both reactions cause additional iodine being consumed, giving a false higher water content.

71

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Good Titration PracticeTM in KF Titration

The following substances can react with iodine:
Ascorbic acid Boric acid, H3BO3 Disulfite, S2O5 2– Hydroxide, OH– Mercaptans, R-SH Peroxide, R-O-O-R Sulfite, SO3 Tin(II) salts
2–

Arsenite, AsO2 – Tetraborate, B4O7 2– Iron(III) salts Hydrogencarbonate, HCO3– Nitrite, NO2
– 2– 2–

Arsenate, AsO4 3– Carbonate, CO3 2– Hydrazine, N2H4, and its derivatives Copper(I) salts Oxides, e.g. CaO, MgO, MnO2 Silanols, R3-Si-OH Thiosulfate, S2O3 2–

Selenite, SeO3 Tellurite, TeO3

Solution: The Karl Fischer titration for the majority of these substances can be performed with the aid of the drying oven, or also by performing an external extraction.

9.4 Example: reevaluation of side reactions
The water content obtained is too high if side reactions previously described have occurred. This can also be the case if a drying oven is used, and the sample slowly decomposes. Nevertheless, the correct result can be reevaluated by graphical extrapolation. Example: Water determination in red polypropylene fibers.
µg water

250 °C 160 °C 120 °C

300 200
115 mg 640 ppm

100

0

5

10

15

20 min

The determination was carried out for a period of 20 minutes (max. time) with the drying oven set to 120 °C, 160 °C and 250 °C. The following results were obtained:

120 °C 1186 ppm

160°C 1442 ppm

280°C 1955 ppm

The volume-time curve clearly indicates the occurrence of a side reaction, which becomes faster with increasing the temperature. The "water content" increases with temperature. By reevaluation using the LabX® titration PC software the actual water content can be obtained by extrapolating the titration curve to time t = 0 min (green dotted lines). The content is 115 mg water; this corresponds to a water content of 640 ppm for a sample weight of 0.18 g. The extrapolated result was confirmed by an external extraction in methanol. In fact, the result obtained with this method was 610 ppm.

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1 Coulometry Problem Possible causes and action to take Anolyte is not bright yellow but dark yellow to brown Drift is too high after the pretitration of a fresh anolyte .Replace molecular sieves and silica gel in drying tube .Use higher oven temperature . e. drift stop as termination parameter.g.Check whether titration stand is completely tight.Measurement electrode is not plugged in .METTLER TOLEDO Good Titration PracticeTM in KF Titration 10 Troubleshooting 10. Water distribution in the sample is not homogeneous . increase t(max) Wrong control parameters .Check whether titration stand is completely tight.Use a different method Oven: water not completely vaporized .Level of anolyte should be higher than that of the catholyte . 1 mg water per sample is present. if possible increase amount of sample Wrong sample preparation and sample addition .Higher oven temperature .Clean the platinum pins of the measurement electrode with paper tissue . drift stop .Lengthen vaporization time (increase t max) .Use t(max) as termination parameter .Homogenize sample. especially at low water content (< 1000 ppm) 73 .Measurement electrode is faulty Titration stand not protected against moisture .Replace silica gel and molecular sieve in the gas drying unit The drift remains too high during standby titration Drift is too high after the titration of a sample Side reaction with the anolyte . . .Use smaller sample Long titration time.Increase amount of sample to ensure that approx.Increase vaporization time.Increase end point Oven: water vaporizes very slowly and irregularly .Clean titration cell and generator electrode and dry at 50 – 80 °C .The repeatability is strongly dependent on suitable sample preparation and sample addition.Add a small amount of one-component KF titrant to the catholyte.Increase value for rel.Grease the tapered joints Moisture from cathode compartment and diaphragm .Replace anolyte Amount of sample too small .Replace anolyte . titration never ends Very long pretitration Poor repeatability Wet anolyte . . Oven: .Use rel.

Use higher oven temperature .Add chloroform or another solvent (maximum of 30%) to the anolyte to dissolve the sample Oven: . If the sample preparation and addition is not done carefully. at 170 °C. bad repeatability With water standard 1. Anolyte has too low conductifity .Use smaller sample size Values too high The titration was too fast → overtitration .Extend tmin (minimum titration time) Incomplete sample addition .Use fix generator current 100 mA . Sample not dissolved (emulsion) . . Checking drying oven Out of limits.Clean titration cell and measurement electrode Poor sample preparation and addition Samples of low water content (< 1000 ppm) are always hygroscopic. contamination with atmospheric moisture occurs. . check generator electrode. For samples with very low water content < 30 ppm .Reduce the value for rel.Replace anolyte .3 g Generator electrode is contaminated The black cover cannot be removed. if it is defective.Use start cautious Oven: . drift stop .Too high value: see above “too high value” . do not splash to the walls of the cell.1 mg/g . the Coulometer must be adjusted With water Standard KF Oven 1 %. 10 – 15 minutes .0.Check drift and blank value .METTLER TOLEDO Good Titration PracticeTM in KF Titration Problem Possible causes and action to take Values too low The titration was terminated too soon .Use back weighing.Too low value: see above “too low value” if this does not help.Sample not thermal stable: Use lower oven temperature .Replace or change the anolyte .Lengthen vaporization time (increase t max) . bad repeatability Platinum parts of the generator are colored black Warning: “Conductivity too low” 74 .use a bigger sample size up to 0.Sample is oxidized: use nitrogen as a purge gas Checking coulometer Out of limits.Replace or repaire generator electrode. It has no influence to the result.0 or 0.2 .Replace anolyte If this doesn’t help.Add sample into KF reagents.

drying oven.Increase endpoint potential Oven: water vaporizes very slowly and irregularly .Homogenize sample.Clean platinum pins of the electrode with a paper towel.Replace molecular sieves and silica gel in drying tube . e.g. titration never ends Wrong termination parameters . etc. .Shake titration vessel The drift remains too high during standby titration Titration stand not protected against moisture . increase t(max) Long titration time. e.Reduce sample size Poor repeatability of the results Amount of sample too small . .2 Volumetric Karl Fischer Titration Problem Possible causes and action to take Titrated solution is dark Drift too high after pretitration of fresh solvent Overtitration .METTLER TOLEDO Good Titration PracticeTM in KF Titration 10.see above Oven: .Extend tmax (maximum titration time) .Replace silica gel and molecular sieve in the gas drying unit Drift too high after titration of a sample The sample has not completely dissolved and continuously releases water .Check whether titration stand is completely tight. 75 . Oven: water is not completely vaporized .Increase amount of sample to ensure 10 mg water per sample. Low water content (<1000 ppm)! . Side reaction of the sample with the KF reagent .Increase value for relative drift stop. .Grease the tapered joints Condition Titration stand . external extraction.Use t(max) as termination parameter .Extend vaporization time (increase t max) .Use higher oven temperature .Use different method. drift stop" as a termination parameter.Check and optimize control parameters.Increase vaporization time.The repeatability is strongly dependent on suitable sample preparation and sample addition.Use longer mixing time or different solvents which dissolves the sample or extracts the water quicker. Wrong control parameters . if possible increase amount of sample. Titration stand not protected against moisture . Water distribution in the sample not homogeneous .g.Increase oven temperature .Use "Rel.

bad repeatability 76 .0 is a simpler and a more dependable method. The concentration determination is correct only if the di-sodium tartrate has completely dissolved.4 g Increasing value in the concentration determination with di-sodium tartrate Checking drying oven Out of limits.Reduce dVmax and dVmax factor.Change solvent.METTLER TOLEDO Good Titration PracticeTM in KF Titration Problem Possible causes and action to take Values too low The titration was terminated too soon .Samples of low water content (<1000 ppm) are always hygroscopic.12 g in 40 mL.Extend tmin (minimum titration time) Incomplete sample addition .Use back weighing.Increase sample size up to 0.Use higher oven temperature . Sample not dissolved .Sample is not thermally stable: Use lower oven temperature . which dissolves the sample. Determination of the concentration using di-sodium tartrate or Water Standard 10. For samples with low water content < 400 ppm . 0.Extend vaporization time (increase t max) .Reduce the value for rel. drift stop . With water Standard KF Oven 5. If the sample preparation and addition is done carefully.Check drift and blank value .Use titrant with 2 or 1 mg/mL Oven: .Sample is oxidized: use nitrogen as a purge gas The results in a series are continuously decreasing Very slow titration with twocomponent titrant Wrong or greatly fluctuating values in the concentration determination with water Dissolving capacity of the solvent is exhausted . Water as standard requires practice The use of water for the concentration determination requires experience to obtain repeatable and accurate results.Replace the solvent frequently.Replace solvent . Oven: . Di-sodium tartrate has only limited solubility In methanol max. Poor sample preparation and addition . . No more sulfur dioxide in the solvent .55 % at 220 °C. contamination with atmospheric moisture occurs.Reduce sample size Single values too high Control parameters too fast (= slight overtitration) .Change solvent or use fresh solvent after every sample. 15 – 20 minutes .Add chloroform or other solvent to methanol.

C0 Esters Carboxylic acid ester R-COOR´ Carbonic anhydride ROCOOR´ 77 .1. indole.V5 C20 Ethers Linear and cyclic V2. C0 V2. V4 C20 V15 C20 V0.V4.V5 C20.1 Organic Chemicals Substance Acetals Aldehydes Mono-/polyalcohols Amines Examples R1-CH-(OR2)2 Chlorobenzaldehyde.V3. oxalic acid Oxidizable with iodine: ascorbic acid V2.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11 Karl Fischer Titration: The Method at a Glance 11. anthracene.V3. C0 Peroxides V2. C24 Hydrocarbons > C12 Biphenyl.V3. V3. toluidine Oxidizable with iodine: aminophenol Method V2. nitrobenzaldehyde > C12 Stearyl alcohol.V5 C20. V5 C20 V2. V3.V4.V4. C20 V11 C0 V2. stearamide Weakly acidic: benzoic acid Strongly acidic: malonic acid. diphenylmethanol Weakly basic pKa >8: Imidazole. nitrotoluene. C0 Sulfur compounds Phenols V0. R-I R-NCO Benzophenone Method V2. V4 C20 V2 C20 Substance Halogenated hydrocarbons Isocyanates Ketones Examples R-Cl. bitumen V4. o-cresol Side reaction: naphthol. V4 C20 V2. aminophenol Aromatic/aliphatic sulfonic acids sulfides R-S-R´ disulfides R-SS-R´ thiocyanates R-SCN V0.C22 V2.g. nitrochlorobenzene Dialkylperoxide R-OO-R Alkylperoxide R-OOH Diacyl peroxide V0. naphthalene > C20 Tar.V4 C20 Carbamates Carboxylic acid amides Mono-/polycarboxylic acids RO-CONH2 R-CONR´. e.V3 C20 di-Nitrobenzene.pyren e.V7 V2. C0 V2 C20 V15 Low pKa value: phenol.V4. anisidine.V8 C20 V10. cresol.1 Solid samples 11.: benzamide. salicylic acid High pKa value: 2-chlorophenol.C22 V16 C0 V10 C0 Nitrocompounds V3. carbazole Strongly basic: aminopyridine Reaction with methanol: naphthylamine. V4 C20 Mercaptans V0. V4 V2. R-Br. V3.

C32 V15. herbicides Soluble: wool dyes. CaO NaCl.: Na3PO4 Silicon oxide. KOH MgO. disinfectants Salves. C32 V31 C32 Thiosulfates Tin(II)salts Na2S2O3. V32 C21. polyurethane. HBO3 . V31 C20. C34 V2. NH4NO3 Nitrites NaNO2 11. e. polystyrene. etc. NaHCO3 Na2CO3 B2O3 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. H3BO3 NaOH.g.1.1. KJ. V8 Cosmetics Creams. fungicides. NaAsO2 KHCO3 . V31 C32 V2. polypropylene. V32 C20.3 Technical products – organic Substance Agrochemicals Dyes Examples Method V2 Substance Petrochemicals Examples Method V12 C0 V7 V5. dispersion dyes Waxes. ZnSO4 V2. Na2HPO4 tert. V5 V5 V2 V20 V2 V5 V30. V31 C20. indicator dyes. 78 . V32 C20. PVC. Silicon dioxide Silanols R3Si(OH) Na2SO4. V30 Insecticides. V5 V12 V2 V40. C32 V31 C32 Sulfates Silicon compounds Substance Phosphates Examples Method V2. V32 C21. NaSO3 Na2S2O5 SnCl2 Nitrates NaNO3 . Insoluble: pigments. Phosphate. poly-amides. CaCl2 . creams Suppositories Tablets Lyophilized preparations V2 V4. C34 V2. V31 C20. oxides Halogenides Examples Method V30 C30 V34 C32 V31 C32 V21. lotion Lipstick Soaps Toothpaste V4. V31 C31.C40 V2 Adhesives All-purpose glue. ski wax Tar. paraffins: shoepolish. etc. MgCl2 Cu(I) salts: CuCl2 NaH2PO4 . bitumen lubricating grease. C34 V31 C33 V2. C32 Pharmaceuticals Antibiotics. multipurpose grease V2 V2. glue stick Rubber cement Textile auxiliaries Surfactants powder optical brightener Plastics Polymers Polyethylene. C34 V10 Na2HAsO3 .2 Inorganic chemicals Substance Arsenic compounds Bicarbonates carbonates Boron compounds Hydroxides.

inorganic Substance Building materials Fertilizers Examples Method V32 (C34) V6 Substance Minerals Detergents Examples Method V32 V30.1. (V25) V22. meat spread. dried vegetables and fruits Hazelnuts. tea. rye. sea salt Total water: plain salt. tobacco. (V30) Cheese. coffee beans.1. wheat. wood Cellulose powder Wool. V21 Mortar. noodles. V23 Vegetable products V22. noodles. C30 V2 V20 Paper. mixed spice Mustard Adherent moisture: plain salt. hardened fat V4. candy. V23 Cacao. mayonnaise Shortening. corn. margerine. jellied fruits.4 Technical products . caramel. perborates) without brightener Total water V30 V2 11. plaster. curry. silk 11. jam Honey. V5 V5 Sugar and sugar products V13 V13 Sugar: total water cont. broth Biscuits.almonds instant coffee Fats Butter. gummi bears. (V5) V6 C23 V32 C34 V8 V2 V6 V5 79 . ice cream Dried albumen Powdered milk V2 V13 V2.6 Food Substance Protein products Examples Method V23 Substance Grains and starchy foods Examples Method V13. instant coffee.. almond paste Instant ice tea. V23 V30. jelly Sugar: adherent moisture Chocolate Spices Pepper. sea salt V23 V24. potato chips Potato flakes Dough.1. cement Adherent moisture Zeolites Laundry detergent with brightener (hydroxides. pudding powder. Zwieback.5 Technical natural products Substance Cellulose products Fibrous materials Examples Method V30.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. Zwieback Yogurt.

2.2 Liquid samples 11.1 Organic and inorganic chemicals Substance Acetals Examples Method V1 C1 Substance Hydrocarbons Examples Method V1 C1 Acetal. diamine Easily oxidized with iodine: hydrazine. benzyl alcohol Weakly basic: N-methyl aniline heterocyclic amines pyridine. acrylic acid V15 C0 V1 C1 V1 C1 V1 C1 V1 C1 Acid amides Dimethylformamide Sulfides. nitrotoluene. acetophenone. methylal C1 to C7 hexane. chinoline Strongly basic: alihatic amines N-butylamine. xylene C7 to C14 gasoline. ethyl acetate Methyl chloride. acetic acid > C2 propionic acid. toluidine. dioxane. chlorotoluene Acetone. C1 Sulfurcompounds V1 C1 V0. hexanol. anisole Methyl benzoate. HNO3. ethylal. hydroxylamine V1 C1 V1 C1 Mineral acids V5 C30 V15 C0 Amines H2SO4. isobutane. paraffin Aldehyde Acetaldehyde. hexylamine Reaction with methanol: aniline. cyclohexane. pentane. disulfides sulfonic acids Mercaptans V1.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. benzene. petroleum. C0 Ethers Esters Halogenated hydrocarbons Dimethylether. chlorobenzene. dodecane > C14 heavy oil. toluene. t-butyl chloride. cyclohexene. crude oil. HCl Nitrobenzene. nitrochlorobenzene Acetonitrile V16 C0 Nitrocompounds V1 C1 V10 C0 Nitriles V1 C1 V0 C0 Peroxides H2O2 V15 Carboxylic acids C1 to C2 formic acid. benzaldehyde V11 C0 saturated and unsaturated V4 C1 Alcohols Propanol. methylethylketone Ketones V10 C10 80 .

fungicides Acrylic enamels Emulsions in solvents V1 V1 V29 V4 C1 V7 V4 C1 V4 C1 Agrochemicals (sprays): insecticides Synthetic enamels Foods: salad oil. transformer oil. condensed milk Tensides and detergents Agrochemicals (sprays): herbicides.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.3. refer to chapter 11. brake fluid. cream. massage oil Vegetable oils Technical oils Hydraulic oil. sample input and titration methods. 81 . tinctures Cosmetics: perfume. liquor Pharmaceuticals: extrakts. shampoo Method V1 V1 V1 V1 V4 Tensides and detergents Aqueous emulsions Milk products: milk.2 Foods and technical products Substance Aqueous solutions Examples Foods: spiced sauce: soy sauce beverages: beer. sunflower oil Pharmaceuticals and cosmetics: ethereal oils. wine.2. silicon oil Motor oils V5 C1 V30 C30 For more details on the sample preparation.

dProcedure V1 Direct titration Titrant: Solvent: Stir time: Direct titration Titrant: Solvent: Stir time: two component reagent 5 or 2 mg H2O/mL 40 mL KF solvent 10 s two component reagent 5 or 2 mg H2O/mL 40 mL KF solvent 60 .1 Volumetric methods The methods have been developed using 2-component reagents. These can be also performed using the one-component reagent.120 s Delay time: 7 seconds.3.120 s V2 V3 Direct titration with added 2-propanol Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / propanol 1:1 Stir time: 60 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.120 s Direct titration with added formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 Stir time: 5 .120 s Direct titration with added 1-decanol Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / 1-decanol 1:1 Stir time: 60 . Direct titration with added toluene Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / toluene 1:1 Stir time: 60 .10 minutes V4 V5 V6 V7 V8 V10 V11 V12 82 .120 s Direct titration with added chloroform Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: KF solvent / chloroform 1:1 to 1:2 Stir time: 60 .3 Titration Methods 11. reagent 5 mg H2O/mL for ketone und aldehyde Solvent: 40 mL KF solvent for ketone und aldehyde Stir time: 30 – 60 s Direct titration methanol free Titrant: two comp.120 s Direct titration with added chloroform Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / chloroform 1:5 Stir time: 60 . In this case methanol is used as a solvent.10 minutes Direct titration methanol free Titrant: two comp. reagent 5 mg H2O/mL for ketone und aldehyde Solvent: 40 mL KF solvent for ketone und aldehyde Start immediately (autostart) Direct titration with heat (at 50°C) Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent Stir time: 5 .

220°C Titrant: two component reagent 5 or 2mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .20 min With drying oven at 300°C Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .15 minutes Direct titration with neutralization Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent and 20 mL buffer or 7g imidazole Stir time: 60 . Titrant: two component reagent 2 mg H2O/mL Solvent: 50 mL KF solvent Side reaction: KF titration not possible V15 V16 V20 V21 V22 V23 V24 V25 V29 V30 V31 V32 V40 V0 83 .20 min With drying oven at 160 . Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with methanol at 50 °C Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with 1-decanol/formamide 1:1 Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with 1-decanol/formamide/methanol 8:2:1 Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 With drying oven at 110 . 50°C Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 Stir time: 10 .20 min Special method for lyophilized preparations Dissolve sample in septum flask with 10-20 mL titrated solvent and inject entire solution into titration cell and titrate.150°C Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .METTLER TOLEDO Good Titration PracticeTM in KF Titration V13 Direct titration with added formamide and heat.120 s Direct titration with neutralization Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent and 5 g benzoic acid Stir time: 1-2 minutes External extraction with methanol at room temperature Titrant: two component reagent 5 mgH2O/mL Solvent: 30 mL KF solvent External extraction with methanol at room temperature in sonicator Remove aliquots of extraction solution over membrane filter with syringe.

3. Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Coulometric determination not possible C10 C20 C21 C22 C23 C24 C30 C31 C32 C33 C34 C40 C0 84 . Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with 1-decanol or external dissolution in 1-decanol Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with chloroform or external dissolution in chloroform Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction or external dissolution in chloroform (methanol free) Anolyte: 100 mL anode reagent for ketones Catholyte: 5 mL cathode reagent for ketones With drying oven at 110-130°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 140-150°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 160-190°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 200-250°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 300°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes Special method for lyophilized preparations Dissolve sample in septum flask with 10-20 mL titrated anolyte and inject entire solution into titration cell and titrate.2 Coulometric methods Method C1 Procedure Direct titration Anolyte: Catholyte: 100 mL anode reagent 5 mL cathode reagent C5 Direct titration with added chloroform Anolyte: 70 mL anode reagent and 30 mL chloroform Catholyte: 5 mL cathode reagent Direct titration methanol free Anolyte: 100 mL anode reagent for ketones Catholyte: 5 mL cathode reagent for ketones External extraction with methanol or external dissolution in methanol Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with Methanol in sonicator Remove aliquots of extraction solution over membrane filter with syringe.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.

8 mm ) Fill in backend of syringe Procedure Grind in sealed.5 mm or without needle. meat grinder. shoepolish Creams. coffee. active ingredients Na-tartrate S9 S12 11. Dissolve sample or extract water. S2 S1. Homogenize sample well. 1-decanol. ice cream. bitumen Method S7. brittle Soft. SiO2 Salts. Zwieback Dried vegetables and fruits. or up to approx. almonds. S3 S2.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. Break and disperse with high-speed mixer (up to 24000 cpm) in external extraction solvent (methanol.: CaCO3 . S11 S6. Let solids settle and remove aliquot of remaining solution with syringe. tea. chocolate Method S1 S1. Melt sample. gummi bears. pepper. S5 S10 S8 Paraffins. formamide). brittle Hard natural products Fibrous natural products Tenacious products Soft products Hard. honey. yogurt Salts. broth Hardened fat. Stir. After sample removal keep sample sealed. S10 S2. No further preparation necessary.) Homogenize sample well. napthalene. S11 S4. Inject into titration cell. (Pre-heat syringe with hair dryer or in drying oven. noodles. rocks e. shake or sonicate. Pulverize with mortar. cristalline products Wheat.1 Solids: Characteristics Property Very hard Hard.2 Solids: Sample input Method S1 S2 S3 S4 S5 S6 S7 Sample input finely ground sample with weighing boat finely ground sample with weighing boat finely ground sample with weighing boat with spatula with spatula or weighing boat with spatula or weighing boat with spatula Do not use syringe. jelly. pastes Pulverized soluble Salves. Cut in small pieces with scissors or knife. margarine Phenols. After sample removal keep sample sealed. meat Jellied fruits.4. greasy Soft. greasy Examples Minerals.g. At room temp.g. 1-decanol. Pulverize with mixer. In external extraction solvent (methanol. for very thick pastes drill hole in bottom of syringe. cooled analysis mill. S10 S11 S4. S3 S10. formamide). potato flakes Tar. wool.) S8 S9 S10 syringe with needle Ø 0. almond paste. tobacco. Press through small holes e. creams gel. the moisture will be pressed out with pre-heated syringe (with needle Ø 0.4. S10 S11 S10. (Select stir time so that sample dissolves completely. S8 S10 Property Soft. resinous Waxes Examples Butter. 60° C.4 Sample preparation and input 11. Use grate to reduce size. paper. Use syringe with needle Ø 1.8 mm S11 S12 syringe without needle (Fill very thick samples in back of syringe) weighing boat 85 . silk Cheese.

glycerine Hexane.4. toluene. acetic acid Silicon oil. average moisture content High moisture content Inhomogeneous (> 50%) (< 1000 ppm) 5 . after-shave Beverages.Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.Cool sample to approx. aqueous emulsions Acrylic enamels.4.Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe. Samples with high moisture content (> 50%) Rinse syringe with sample 2-3 times. petroleum.8 mm) to remove fresh sample from sample flask and inject this into titration cell through septum or needle hole of three-hole adapter. cream Method L1 L2 L3 L4 L4 L1 L5 L6 11. H2SO4. Hygroscopic sample or low moisture content (< 1000 ppm) . 11.Homogenize thoroughly by shaking or stirring prior to sample removal.15 °C . crude oil.5 Accessories for sample input Syringe Injection needle Weighing boat. gasoline. milk.8 mm) Injection with syringe (without or with needle Ø 1. . acetone. . .8 mm) Inhomogeneous emulsions . acetone. Turbid liquid sample Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.8 mm ME-71482 ME-71484 Septum NS24 ME-23950 Three-hole adapter ME-23982 86 .2 mm ME-71483 ME-23951 ME-51107668 10 mL 0.3 Liquids: Characteristics Property Liquid Turbid Low boiling point Hygroscopic Low moisture content Non-hygroscopic. L2 L3 L4 L5 Injection with syringe L6 Injection with syringe after sample homogenization (with needle Ø 0. glycerine Acetaldehyde Methanol. detergents. 0°C in ice bath. For each titration use 1 mL syringe (with needle Ø 0.4 Liquids: Sample input Method L1 Sample input Injection with syringe (with needle Ø 0. Boiling point 5 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.Rinse syringe with sample 2-3 times (pull up and discard) and condition for 5 minutes. synthetic enamels. . glass Visco-Spoon™ 1 mL ME-71492 1.4.Remove sample immediately.8 mm) Injection with syringe Procedure Fluid liquid sample Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.The pressure loss during sample removal must be compensated with dried air.Keep sample in a septum flask.5 mm) Injection with syringe after cooling sample (with needle Ø 0.8 mm).Inject sample into titration cell through septum or needle hole of three-hole adapter with 10 mL syringe (with needle Ø 0. salad oil Perfume.15°C Examples Propanol. . .

Thesis University of Hannover. E. KOK. E. 139-147 (2000).C. 215 – 219 (1959). 31 (2). 256-260 (1989) (in German).. W. „Karl-Fischer Reagentien ohne Pyridin..METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. J. Chem.. “Analytical Procedures Employing Karl Fischer Reagent I. SCHOLZ. „Kinetics and stoichiometry in the Karl Fischer solution“. P. 305-315 (1976). J. SCHOLZ. Fresenius Z. 395-403 (1977). Ed.396 (1935)..2412 (1939). Chem. HOPFKINSON. Chem. Part IV. S. Chem. Angew.. Anal. 394 .. 15 (4). J.. MITCHELL jr. “Mechanism and reaction rate of the Karl Fischer titration reaction. “Mechanism and reaction rate of the Karl Fischer titration reaction. F. Fresenius J. 272 – 274 (1943). WÜNSCH. W. Eng. 16-21 (1989) (in German). “Mechanism and reaction rate of the Karl Fischer titration reaction.. K. Chem. 1. Rotating ring disk electrode meassurement“... Anal. BOYD. 394 . 94. Diploma-Thesis at the University of Hannover / Germany. J.J. “Karl-Fischer Reagentien ohne Pyridin“. 203 . BUNSEN. Einkomponenten Reagentien“. 71..C.. Chem 368. “Determination of Water by Titration with Coulometrically Generated Karl Fischer Reagents”. VERHOFF. „Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern“. 334. E. See literature references in: EBERIUS.4. Neue Eichsubstanzen“. 705-717 (1976).C. Chem.W. J. 312. D. Auflage. Part I.M. Ind. 48. Part II. BARENDRECHT. J. 1988 (in German). Fresenius Z. J. „Mechanism and reaction rate of the Karl Fischer titration reaction. Analytical implications”. 2407 . SEUBERT A. “Stöchiometrie und Kinetik der Karl-Fischer –Reaktion in Methanol als Reaktionsmedium”.. [8] SCHOLZ. Electroanal. 75. Anal. 86. BARENDRECHT. Zweikomponenten Reagentien mit Imidazol“. Chem. W.. Rotating ring disk electrode meassurement . Chem.. E. 306. E. Chem. First and second order catalytic currents at a rotating disk electrode“. E. 407-415 (1978). G. Anal. 86. J. Chim. 75-80 (1978). J.. 93. BRYANT. Fresenius Z. S. Part V.S. 61.. Anal.. [10] GRÜNKE. Th. E. VERHOFF. Anal. J. „Karl-Fischer Reagentien ohne Pyridin. Z. Chem. Anal. Part III. Fresenius Z. Chem. “Mechanism and reaction rate of the Karl Fischer titration reaction.. [9] WÜNSCH. E.comparison with the aqueous system“. Amer.. BARENDRECHT.. „The Dead-Stop End Point – As Applied to the Karl Fischer Method for Determining Moisture“. Electroanal. PhD. GRÜNKE.. Fres. Both publications from: SEUBERT. 1999 (in German). SCHOLZ. 123-125 (1981). Anal. 460-464 (1982). Verlag Chemie Weinheim (1954) / (in German). E. Anal. 309. „Wasserbestimmung mit Karl-Fischer-Lösung“. “Reaktionsmechanismen in der Karl-Fischer-Lösung“. G. Electroanal. Soc.. Chem. VERHOFF. A.. 30-32 (1981). Anal. VERHOFF. . Z. R.396 (1981). Chem. C. A. WERNIMONT. Chem. SMITH. 265 (1853). „Karl-Fischer Reagentien ohne Pyridin Genauigkeit der Wasserbestimmung“. 334. SEUBERT A. Nature of the Reagent”. WÜNSCH. Electroanal. [3] [4] [5] [6] [7] 87 . „Karl-Fischer Reagentien ohne Pyridin.C. Anal. Liebigs Ann.C. MEYER.207 (1980). J. Fresenius Z. Chem. Potentiometric measurements”. M.6 References [1] [2] FISCHER. COFINO.. G. 309. Fres. G.. 303. “Untersuchungen zur Karl-Fischer-Reaktion”. M. “Nebenreaktionen in Karl-Fischer-Reagenzien ”. Chem. SCHOLZ. VERHOFF.. Acta.

„Untersuchungen einer Karl-Fischer-Reaktion“... DE AGOSTINI A.5 Additional literature HYDRANAL®-Manual. GIT Verlag GmbH. Food Chemistry 96.A. Sigma-Aldrich Laborchemikalien GmbH.. Diploma-Thesis at the University of Hannover / Germany..METTLER TOLEDO Good Titration PracticeTM in KF Titration [11] LANZ. K. SCHÖFFSKI.. WIELAND. „Karl Fischer Titration“. 431-435 (2006). 2006.30918 Seelze / Germany. „Eugen Scholz Reagents for Karl FischerTitration“. 1989 (German) 88 . DE CARO C. E. Darmstadt / Germany. 11. G.. Springer Verlag Berlin. 1984. D. RÜEGG K.. „Wasserbestimmung durch Karl-Fischer-Titration . SCHOLZ. 1985.Theorie und Praxis“. "Coulometric Karl Fischer titration with a diaphragm-free cell: Cell design and applications". M.

Water amount after extraction = Water amount before extraction WTOT•(mL + (mP•WP) ) = WP•mP + WL•mL where Water content in the sample P (% or ppm). WP: This is what we get from the calculation in the KF method.1 Formula for the external extraction Principle: • • The water amount (in grams) after extraction is equal to the water amount before extraction. WTOT : Water content of the supernatant extraction solvent (% or ppm) WL : mL : mP : Thus: 1) 2) 3) 4) 5) 6) 7) For % : C ⋅ [msol + (mext ⋅ R )] = R ⋅ mext + B ⋅ msol R C B msol mext Blank value (water content of the solvent. 89 . % or ppm). For ppm : R (ppm ) = 10 6 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 10 6 − C ⎝ mext since 1 = 106 ppm. The sample P used for the extraction is not dissolved. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent C ⋅ msol + C ⋅ mext ⋅ R = R ⋅ mext + B ⋅ msol C ⋅ mext ⋅ R − R ⋅ mext = B ⋅ msol − C ⋅ msol R ⋅ (C ⋅ mext − mext ) = B ⋅ msol − C ⋅ msol R= 1 ⋅ (B ⋅ msol − C ⋅ msol ) (mext ⋅ (C − 1)) R= R= 1 ⋅ (C ⋅ msol − B ⋅ msol ) (mext ⋅ (1 − C )) since 1 1 =− 1− C C −1 1 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 1 − C ⎝ mext R (%) = 100 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 100 − C ⎝ mext since 1 = 100%.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12 Appendix 12.

90 . the total volume is increased.1 mg/g (100 ppm) SIGMA-ALDRICH HYDRANAL®-Water Standard 1. The sample P used for the external dissolution is completely dissolved into the solvent.3 Standards for Karl Fischer coulometry a) For direct measurements: VWR/VWR/MERCK APURA water standard 0.01% VWR/VWR/MERCK APURA water standard 0. Thus.55% (potassium citrate monohydrate) The water content is declared on a test certificate supplied with every vial.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. in % or ppm.00 mg/g (1000 ppm) b) For measurements with an oven: VWR/VWR/MERCK APURA Water standard oven 1% (tungstate) SIGMA-ALDRICH HYDRANAL®-Water Standard KF-Oven 5. Blank value (water content in% or ppm) of the solvent. Total water content (sample + solvent).1% SIGMA-ALDRICH HYDRANAL®-Water Standard 0. ppm ) = C ⋅ ⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ 12. Water amount after dissolution = Water amount before before dissolution WTOT•(mL + mP) = WP•mP + WL•mL where WP: WTOT : WL : mL : mP : Thus: 1) 2) 3) 4) C ⋅ [msol + mext ] = R ⋅ mext + B ⋅ msol Water content in the sample P (% or ppm) This is what we get from the calculation in the KF method. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent R C B msol mext C ⋅ msol + C ⋅ mext = R ⋅ mext + B ⋅ msol R ⋅ mext = C ⋅ msol + C ⋅ mext − B ⋅ msol ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R = C ⋅⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ For % and ppm: ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R(%.2 Formula for the external dissolution Principle: The water amount (in grams) determined by titration is the sum of the water amounts present in the solvent and in the sample.

an emulsion is formed.2 For samples that are poorely soluble in methanol or ethanol These include: etherial oils. hydrocarbons (C10 to C20). ethers. chlorinated hydrocarbons (up to C10). For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat AG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) Ethanol-based reagents: anolyte: HYDRANAL® Coulomat E (SIGMA-ALDRICH) catholyte: HYDRANAL® Coulomat E (SIGMA-ALDRICH) Methanol-based reagents: electrolyte:HYDRANAL® Coulomat AD (SIGMA-ALDRICH) - For cells without diaphragm: - APURA combiCoulomat fritless (VWR/VWR/MERCK) 12. the water content determined is lower than the actual water content of the sample. part of the water content is not measured. ointments. This is limited to a maximum of 30% to prevent the conductivity from falling too low. A number of different anolytes are available to dissolve the various types of samples encountered in practice. In this case.4.1 For samples that are soluble in methanol or ethanol These include: hydrocarbons (up to C10). This means that if an emulsion is formed in the anolyte.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. acetamide. esters. more solvent can be added to the anolyte. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat AG-H (SIGMA-ALDRICH) contains approx. etc. edible oils. Alternatively. etc.4 Reagents and solvents for coulometric analysis To determine its total water content. If the sample does not completely dissolve. 12. Octanol or hexanol can be added to the anolyte to improve the solubility of these samples. the anolyte must be immediately replaced.e. i.4. the sample must completely dissolve in the anolyte. alcohols. 30% hexanol APURA combiCoulomat frit (VWR/VWR/MERCK) + 30% hexanol catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit For cells without diaphragm: 91 . nitrocompounds.

4. For cells with diaphragm: Methanol-free reagents: anolyte: HYDRANAL® Coulomat AK (SIGMA-ALDRICH) catholyte: HYDRANAL® Coulomat CG-K (SIGMA-ALDRICH) Methanol-free reagents: electrolyte: HYDRANAL® Coulomat AK (SIGMA-ALDRICH) When changing from normal KF anolytes to ketone reagents. hydrocarbons (above C20). For cells without diaphragm: - Notes on ketones: - - 92 .4. Acetal formation: Ketal formation: CH3COH + 2 CH3OH → (CH3)2CO + 2 CH3OH → CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O Special methanol-free reagents must be used for these substances. the entire titration cell must be thoroughly cleaned because even traces of methanol may cause serious interferences. transformer oils. Chloroform must be added to the anolyte to ensure the solubility of these samples.4 For ketones and aldehydes Ketones and aldehydes react with methanol to form a ketal or an acetal and water. etc.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-based reagents: electrolyte: HYDRANAL® Coulomat AD (SIGMA-ALDRICH) + 20% hexanol APURA CombiCoulomat fritless (VWR/VWR/MERCK) + 20% hexanol 12. If you measure ketones regularly.3 For samples that are insoluble in methanol or ethanol These include: petroleum oils. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat A (SIGMA-ALDRICH) + 20% chloroform HYDRANAL® Coulomat AG (SIGMA-ALDRICH) + 30% chloroform APURA combiCoulomat frit (VWR/VWR/MERCK) + 30% chloroform catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) Methanol-based reagents: electrolyte: HYDRANAL® Coulomat AD (SIGMA-ALDRICH) + 30% chloroform APURA combiCoulomat fritless (VWR/VWR/MERCK) + 30% chloroform For cells without diaphragm: - 12. we recommend the use of a second titration cell. silicone oils. This is limited to a maximum of 30% in order to prevent the conductivity from becoming too low.

Use the HYDRANAL® buffer (SIGMA-ALDRICH). Measurement with moistened indicator paper also gives an approximate indication of the pH value of the anolyte.g. Short chain aldehydes (e. The measurement should not be performed in the titration cell because the electrode introduces too much water. - For acidic samples. the more important the effect of side reactions becomes. benzaldehyde) can also be determined by coulometric KF titration. With Karl Fischer titrations of acidic and basic samples. The use of imidazole increases the pH value in the anolyte. Basic samples must be neutralized with salicylic acid or benzoic acid.g. In these cases the pH value of the anolyte should be measured.2). however. The larger the sample. 90 mL of anolyte and 5 g salicylic acid or benzoic acid. acetic acid. with reactive ketones such as cyclohexanone use only 0. Choose relatively small samples (approx. formic acid. the drift increases from sample to sample so strongly that the determination of the endpoint becomes difficult. the substances can.e. 1 mL). After a longer standby period.5 For acids and bases (pH value) A noisy titration or a sluggish end point can indicate a pH shift. take an aliquot of anolyte from the titration cell.4. easily be measured with volumetric KF determination. Fill the anode compartment with approx.METTLER TOLEDO Good Titration PracticeTM in KF Titration - If you have titrated a number of ketone samples. - - Notes on aldehydes: - - 12. This is why one should wait for the reverse cleavage reaction of the bisulfide compound before aborting the titration (ensure that the drift drops down again to the initial value). The special reagent for ketones can also be used for other samples.: - For basic samples. Measure the pH with a glass electrode adjusted with aqueous buffers. i.5 to 7 (see Section 1.5 mL. e. It should be noted that the bisulfide-addition reaction is very strong with aromatic aldehydes. 80 mL of anolyte and 20 mL HYDRANAL® buffer. e. To do this. It is important to note that alcohols that react with ketones should not be titrated in this reagent. Fill the anode compartment with approx. amines: - 93 . acetaldehyde) are oxidized at the anode with the formation of water. the drift is higher because of the very slow side reaction.2 mL to 0. it is possible that the anolyte is exhausted after a few days even though no further titrations have been performed.g. etc. Aromatic aldehydes (e. the pH value of the anolyte must be adjusted to the range 5.g. Coulometric KF titration cannot be used to determine these compounds.

12.1 For samples soluble in methanol or ethanol These include: hydrocarbons (to C10). i. etc. chlorinated hydrocarbons (to C10). the result determined is lower than the actual water content. the anolyte must be immediately replaced.0 mg/g (1000 ppm) SIGMA-ALDRICH HYDRANAL®-Water Standard 10. etc. A number of different anolytes are available to dissolve the various types of samples encountered in practice. ointments.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12.1% VWR/VWR/MERCK APURA® water standard 1% SIGMA-ALDRICH HYDRANAL®-Water Standard 1. edible oils.2 For samples poorly soluble in methanol or ethanol These include: etherial oils. If it does not completely dissolve.e.6. an emulsion is formed. nitrocompounds.5 Water Standards for Karl Fischer volumetric titration a) For direct measurements: VWR/VWR/VWR/MERCK APURA® water standard 0. In this case. hydrocarbons (C10 to C20). Octanol or hexanol can be added to the anolyte to improve the solubility of these samples. This is limited to a maximum of 50%. more solvent can be added to the anolyte 12.6. In this case. alcohols. One-component reagents: 94 . acetamide. The water content is declared on a test certificate supplied with every vial. ethers. esters.0 mg/g (10’000 ppm) b) For measurements with an oven: VWR/VWR/MERCK APURA Water standard oven 1% (tungstate) SIGMA-ALDRICH HYDRANAL®-Water Standard KF-Oven 5.6 Titrants and solvents for volumetric analysis The sample must be completely dissolved in the anolyte to determine the total water content. part of the water content is not measured.55% (potassium citrate monohydrate). Alternatively. One-component reagents: Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: Dry methanol Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent Ethanol-based: Titrant: HYDRANAL® Titrant E Solvent: HYDRANAL® Solvent E (SIGMA-ALDRICH) (VWR/Merck) Two-component reagents: (SIGMA-ALDRICH) (VWR/Merck) - (SIGMA-ALDRICH) (SIGMA-ALDRICH) 12.

This is limited to a maximum of 50% in order to prevent the conductivity from becoming too low. silicone oils.4 For ketones and aldehydes Ketones and aldehydes react with methanol to form a ketal.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: HYDRANAL® LipoSolver CM. One-component reagents: 95 . hydrocarbons (above C20). Oil apura® Solvent Oil & Fats (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) 12. Oil apura® Solvent Oil & Fats (SIGMA-ALDRICH) (VWR/Merck) (VWR/Merck) Two-component reagents: - (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) 12. with the formation of water. transformer oils. Chloroform must be added to the anolyte to ensure the solubility of these samples. One-component reagents: Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: HYDRANAL® Solver (Crude) apura® CombiSolvent Fats Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent CM.6. Acetal formation: Ketal formation: CH3COH + 2 CH3OH → CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O (CH3)2CO + 2 CH3OH → Special methanol-free reagents must be used for these substances.3 For samples insoluble in methanol or ethanol These include: petroleum oils. etc. or an acetal. MH apura® CombiSolvent Fats (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) Two-component reagents: Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent CM.6.

If you measure ketones regularly. 80 mL of anolyte and 20 mL HYDRANAL® buffer. Measure the pH with a glass electrode adjusted with aqueous buffers.6. - For acidic samples. the drift increases from sample to sample so strongly that the determination of the endpoint becomes difficult. The larger the sample. the pH value of the anolyte must be adjusted to the range 5. With Karl Fischer titrations of acidic and basic samples.5 mL. amines: 96 .g. It is important to note that alcohols that react with ketones should not be titrated in this reagent.g. we recommend the use of a second titration cell. e. Fill the anode compartment with approx. Coulometric KF titration cannot be used to determine these compounds. formic acid. If you have titrated a number of ketone samples. 1 mL). etc. In these cases the pH value of the anolyte should be measured. easily be measured with volumetric KF determination. e.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-free: Titrant: Solvent: HYDRANAL® Composite 5 K apura® CombiTitrant 5 Keto (SIGMA-ALDRICH) (VWR/Merck) HYDRANAL® Medium K (SIGMA-ALDRICH) HYDRANAL® Working Medium K HYDRANAL® KetoSolver apura® CombiSolvent Keto (VWR/Merck) Notes on ketones: When changing to ketone reagents.5 For acids and bases (pH value) A noisy titration or a sluggish end point can indicate a pH shift. This is why one should wait for the reverse cleavage reaction of the bisulfide compound before aborting the titration (ensure that the drift drops down again to the initial value). Aromatic aldehydes (e. i.2). however. take an aliquot of anolyte from the titration cell. Short chain aldehydes (e. Measurement with moistened indicator paper also gives an approximate indication of the pH value of the anolyte. acetic acid. Use the HYDRANAL® buffer (SIGMA-ALDRICH). To do this.g. benzaldehyde) can also be determined by coulometric KF titration. acetaldehyde) are oxidized at the anode with the formation of water.: - For basic samples. the more important the effect of side reactions becomes. the substances can. with reactive ketones such as cyclohexanone use only 0.2 mL to 0.5 to 7 (see Section 1. the entire titration cell must be thoroughly cleaned because even traces of methanol can cause serious interference.g. Choose relatively small samples (approx. the drift is higher because of the very slow side reaction. The measurement should not be performed in the titration cell because the electrode introduces too much water. The use of imidazole leads to a high pH value in the anolyte.e. - Notes on aldehydes: - - 12. The special reagent for ketones can also be used for other samples. It should be noted that the bisulfide-addition reaction is very strong with aromatic aldehydes.

4 Safety data for the KF-components and auxiliary solvents: sulfur dioxide: iodine: diethyleneglycolmonomethylether: 2-methoxyethanol: MAK-value: 200 ppm MAK-value: 0. Ignition temp. 13 Hazards and waste disposal tips 13.1 One-component reagent Composition: sulfur dioxide. swallowed or allowed to contact skin. Do not let reagent contact skin or eyes. Keep container tightly closed and far removed from open flames or sparks. buffer (imidazole) and solvent (methanol. Irritant when inhaled. buffer (imidazole). Disposal: as an organic solvent. Health hazard when inhaled. 90 mL of anolyte and 5 g salicylic acid or benzoic acid. Poisonous when inhaled or swallowed. oxidant Ignition temp. Safety: flammable to extremely flammable.: 28 °C MAK value: 100 ppm Flammable.: 87 °C Ignition temp. swallowed or allowed to contact skin. 13.: does not burn MAK vlaue: 200 ppm 97 methanol: o-xylene: chloroform: .2 Two-component reagent: Composition: iodine and solvent (methanol. 2-methoxyethanol.1 ppm. Safety: flammable to extremely flammable. tetrachloromethane. sulfur dioxide.3 Reagents for coulometry: Composition: iodine. poisonous when inhaled or swallowed. Skin irritant. Keep away from open flames or sparks. Health hazard when inhaled. Ignition temp. Keep away from open flames or sparks. Potential teratogen. The KF solvent contains: sulfur dioxide. Irritant when inhaled. Disposal: as an organic solvent. Health hazard when inhaled. 2-methoxyethanol). Safety: Highly flammable. and solvent (methanol.: 11 °C MAK value: 200 ppm Highly flammable. Fill the anode compartment with approx. 13. Health hazard upon inhalation. chloroform. swallowed or allowed to contact skin.: 46 °C MAK value: 5 ppm Flammable. Keep container tightly closed. Disposal: as an organic solvent. Irritant when inhaled. 13. Do not let reagent contact skin or eyes. 2methoxyethanol or diethyleneglycolmonomethylether). buffer (imidazole) and solvent (methanol. Do not let reagent contact skin or eyes. Keep container tightly closed.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Basic samples must be neutralized with salicylic acid or benzoic acid. 2methoxyethanol or diethyleneglycolmonomethylether). xylene or trichloroethaylene). iodine. Ignition temp.

: inflammable MAK value: 20 ppm Irritant for skin and eyes. Ignition temp. Ignition temp. Irreversible damage possible. Health hazard upon inhalation 98 . Potential teratogen.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1-decanol: formamide: toluene: Health hazard when inhaled.: 6°C MAK value: 20 ppm Extremely flammable.: 95 °C Irritant for skin and eyes. Ignition temp.

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Switzerland Tel. www. ME-51725145A Markt Support AnaChem .mt. Analytical Sonnenbergstrasse 74 CH-8606 Schwerzenbach. It outlines specific aspects in developing and maintaining a good routine operation with METTLER TOLEDO Compact Coulometric and Volumetric KF as well as Excellence titrators. This brochure specifically focuses on Good Titration Practice in water determination using coulometric and volumetric Karl Fischer Titration. The GTP KF brochure and the application brochure 38 containing dedicated applications on samples from various industry segments. are two powerful tools which are meant to facilitate your daily water determination analyses and to contribute to reliable results over the whole lifetime of your instrument. +41-44 806 77 11 Fax +41-44 806 73 50 Subject to technical changes. method validation.com For more information Mettler-Toledo AG. Evaluation of the appropriate titration system (DQ) i. Installation of the selected analytical system comprising IQ and OQ and training of personnel 3. development of SOPs and maintenance of the validated state of the analytical system. specification of the analytical requirements and purchase decision 2.e. Routine operation including PQ. ©09/2009 Mettler-Toledo AG Printed in Switzerland. evaluation.Good Titration Practice in water determination Good Titration Practice™ (GTP) in general encompasses three important steps: 1.

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